一种模块化合成多取代三氟甲基联烯的方法

1.本发明属于有机合成技术领域，具体涉及一种模块化合成多取代三氟甲基联烯的方法。


背景技术：

2.联烯基团是天然产物结构中的重要结构单元，也是可以广泛转化的重要有机合成中间体，而且引入三氟甲基基团能够显著影响有机分子的理化性质和生物活性，因此发展合成三氟甲基取代的联烯结构的方法学具有重要的研究意义。
3.然而，目前合成三氟甲基取代的联烯方法大多在底物范围、官能团兼容性、原料的易得程度上存在较大问题。


技术实现要素：

4.本发明目的在于克服现有技术存在的缺点与不足，提供一种模块化合成多取代三氟甲基联烯的方法。该方法以2-三氟甲基-1,3-烯炔类化合物、亲电试剂与碳氢化合物为原料，通过光催化的hat(氢原子转移) 过程产生自由基，自由基进攻1,3-烯炔，同时在镍的协同催化下与亲电试剂偶联，实现1,3-烯炔的1,4-双官能团化得到多取代三氟甲基联烯。
5.本发明的目的通过下述技术方案实现：
6.一种模块化合成多取代三氟甲基联烯的方法，包括下述步骤：将2-三氟甲基-1,3-烯炔类化合物、亲电试剂、碳氢化合物、催化剂金属镍络合物、光催化剂十聚钨酸盐、碱金属盐加入到有机溶剂中，在惰性氛围和紫光照射下反应，反应后分离提纯，得到多取代三氟甲基联烯。所述的亲电试剂包括但不限于芳基溴化物、烯基溴化物、炔基溴化物、酰氯。
7.进一步地，所述的模块化合成多取代三氟甲基联烯的方法，包括下述步骤：在惰性气体的保护下，向透明反应容器中加入十聚钨酸盐、金属镍络合物、2-三氟甲基-1,3-烯炔类化合物、亲电试剂、碳氢化合物、碱金属盐以及有机溶剂，封闭反应容器，在紫光灯照射下反应完全，经柱层析分离得到多取代三氟甲基联烯。
8.进一步地，所述的模块化合成多取代三氟甲基联烯的方法的合成反应式如下：
[0009][0010]
优选的，所述的2-三氟甲基-1,3-烯炔类化合物、亲电试剂、碳氢化合物、多取代三氟甲基联烯的结构分别如合成反应式中的式a、b、c、d所示。
[0011]
上述各式中，r为烷基或芳基取代基；e为芳基、乙烯基、酰基或炔基，x为卤素原子；g为被夺走一个氢原子的碳氢化合物，h为碳氢化合物上被夺走的氢原子。
[0012]
优选的，式a所示的2-三氟甲基-1,3-烯炔的r选自如下结构：
[0013][0014]
优选的，式b所示的亲电试剂选自如下结构：
[0015]
[0016][0017]
优选的，式c所示的碳氢化合物选自如下结构：
[0018][0019]
优选的，所述的碱金属盐选自如下无机碱中的一种：磷酸钾、磷酸氢二钾、碳酸钠、碳酸氢钠、碳酸铯；所述的有机溶剂为丙酮、乙腈、二甲亚砜、乙酸乙酯中的一种或多种组成的混合溶剂。
[0020]
优选的，所述的模块化合成多取代三氟甲基联烯的方法中，2-三氟甲基-1,3-烯炔类化合物、亲电试剂、碳氢化合物、十聚钨酸盐、金属镍络合物、碱金属盐的最佳摩尔比为1.2:1.0:10:0.02:0.1:2；亲电试剂的浓度为0.5～0.1mol/l。
[0021]
本发明的优点和有益效果：本发明提供了一种有效的以2-三氟甲基-1,3-烯炔类化合物、亲电试剂、碳氢化合物为原料，金属镍络合物为催化剂，十聚钨酸盐为光催化剂，在惰性气体保护条件下由紫光光照制备各种多取代三氟甲基联烯化合物的方法。该方法可适用于多种含不同取代基的2-三氟甲基-1,3-烯炔类化合物与各种类型亲电试剂(包括但不限于芳基溴化物、烯基溴化物、炔基溴化物、酰氯)，以及各种碳氢键化合物，反应条件温和，操作简便，官能团兼容性强，底物适用性广，原料廉价易得，是一种高效、绿色、廉价合成多取代三氟甲基联烯的方法。
具体实施方式
[0022]
通过下述实施例将有助于理解本发明，但并不限制本发明的内容。
[0023]
实施例1
[0024][0025]
在惰性(氩气)气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1a(47.1mg, 0.24mmol)，4-溴苯甲酸乙酯2a(45.8mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物4(71.9mg,84％yield)。
[0026]1h nmr(600mhz,cdcl3)δ8.05(d,j＝8.4hz,2h),7.43-7.34(m,5h),7.31-7.28(m,2h),4.40(q,j＝ 7.1hz,2h),2.22(d,j＝7.1hz,2h),1.74-1.67(m,2h),1.64-1.60(m,3h),1.57-1.50(m,1h),1.40(t,j＝7.1hz, 3h),1.19-1.08(m,3h),0.94-0.85(m,2h)；
13
c nmr(151mhz,cdcl3)δ204.4(q,j＝4.1hz),166.2,139.7, 134.3,130.1,129.8,128.7,128.5,128.46,128.40,123.6(q,j＝274.9hz),115.6,100.9(q,j＝33.5hz),61.1, 36.3,34.8,33.06,33.05,26.2,25.98,25.96,14.3；
19
f nmr(565mhz,cdcl3)δ-63.46；hrms:(esi)calcd for c
26h28
f3o
2
[m h]

429.2036；found 429.2037.
[0027]
实施例2
[0028][0029]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1b(54.3mg,0.24mmol)， 4-溴苯甲酸乙酯2a(45.8mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w, 390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物5(58.6mg,64％yield)。
[0030]1h nmr(600mhz,cdcl3)δ8.04(d,j＝8.4hz,2h),7.39(d,j＝8.4hz,2h),7.22(d,j＝8.8hz,2h), 6.91(d,j＝8.8hz,2h),4.39(q,j＝7.1hz,2h),3.83(s,3h),2.24-2.16(m,2h),1.74-1.67(m,2h),1.65-1.58 (m,3h),1.57-1.49(m,1h),1.40(t,j＝7.1hz,3h),1.22-1.08(m,3h),0.95-0.84(m,2h)；
13
c nmr(151mhz, cdcl3)δ204.4(q,j＝4.1hz),166.4,159.9,140.2,130.2,129.9,129.8,128.5,126.5,124.7(q,j＝274.3hz), 115.4,114.3,100.7(q,j＝33.5hz),61.2,55.5,36.5,35.0,33.23,33.21,26.4,26.15,26.13,14.5；
19
f nmr(565 mhz,cdcl3)δ-63.48；hrms:(esi)calcd for c
27h30
f3o
3
[m h]

459.2142；found 459.2144.
[0031]
实施例3
[0032][0033]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1c(53.1mg,0.24mmol)， 4-溴苯甲酸乙酯2a(45.8mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w, 390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物6(22.3mg,25％yield)。
[0034]1h nmr(600mhz,cdcl3)δ8.07(d,j＝8.3hz,2h),7.67(d,j＝8.3hz,2h),7.40(d,j＝8.4hz,2h), 7.34(d,j＝8.4hz,2h),4.40(q,j＝7.1hz,2h),2.23(d,j＝7.1hz,2h),1.65-1.60(m,5h),1.54-1.49(m,1h), 1.40(t,j＝7.1hz,3h),1.16-1.08(m,3h),0.92-0.85(m,2h)；
13
c nmr(151mhz,cdcl3)δ204.9(q,j＝4.2 hz),166.0,139.4,138.4,132.6,130.7,130.2,129.0,128.4,123.4(q,j＝275.2hz),118.5,114.6,112.1,102.2(q, j＝33.9hz),61.3,36.4,34.8,33.09,33.07,26.2,26.0,14.4；
19
f nmr(565mhz,cdcl3)δ-63.37；hrms:(esi) calcd for c
27h27
f3no
2
[m h]

454.1988；found 454.1989.
[0035]
实施例4
[0036][0037]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1d(45.6mg,0.24mmol)， 4-溴苯甲酸乙酯2a(45.8mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w, 390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物7(56.6mg,67％yield)。
[0038]1h nmr(600mhz,cdcl3)δ8.01(d,j＝8.4hz,2h),7.41(d,j＝8.4hz,2h),4.38(q,j＝7.1hz,2h), 2.56-2.48(m,2h),2.12(d,j＝7.1hz,2h),1.81-1.70(m,2h),1.70-1.61(m,3h),1.57-1.49(m,2h),1.49-1.42 (m,1h),1.39(t,j＝7.1hz,3h),1.38-1.28(m,4h),1.22-1.09(m,3h),0.90(q,j＝7.1hz,5h)；
13
c nmr(151 mhz,cdcl3)δ204.0(q,j＝4.2hz),166.4,139.8,129.9,129.7,126.4,124.0(q,j＝274.5hz),112.5,100.7(q, j＝33.4hz),61.1,36.5,34.9,33.3,31.5,30.2,27.5,26.4,26.2,26.1,22.6,14.5,14.1；
19
f nmr(565mhz, cdcl3)δ-63.40；hrms:(esi)calcd for c
25h34
f3o
2
[m h]

423.2505；found 423.2510.
[0039]
实施例5
[0040][0041]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1e(55.7mg,0.2mmol)， 4-溴苯甲酸乙酯2a(55.1mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w, 390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物8(57.2mg,56％yield)。
[0042]1h nmr(600mhz,cdcl3)δ8.01(d,j＝8.5hz,2h),7.42(d,j＝8.4hz,2h),4.38(q,j＝7.1hz,2h), 3.83-3.73(m,2h),2.76(t,j＝7.2hz,2h),2.17-2.08(m,2h),1.80-1.60(m,5h),1.51-1.43(m,1h),1.39(t,j＝ 7.1hz,3h),1.23-1.08(m,3h),0.96-0.85(m,2h),0.87(s,9h),0.03(d,j＝4.3hz,6h)；
13
c nmr(151mhz, cdcl3)δ204.2(q,j＝4.2hz),166.4,139.5,130.0,129.8,126.4,123.9(q,j＝274.5hz),109.3,100.8(q,j＝ 33.6hz),61.9,61.2,36.4,35.0,33.6,33.3,33.2,26.4,26.2,26.1,26.0,18.5,14.5,-5.3；
19
f nmr(565mhz, cdcl3)δ-63.35；hrms:(esi)calcd for c
28h42
f3o3si

[m h]

511.2850；found 511.2850.
[0043]
实施例6
[0044][0045]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1f(41.1mg,0.24mmol)， 4-溴苯甲酸乙酯2a(45.8mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w, 390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物9(26.9mg,34％yield)。
[0046]1h nmr(600mhz,cdcl3)δ8.02(d,j＝8.5hz,2h),7.42(d,j＝8.5hz,2h),4.37(q,j＝7.1hz,2h), 3.89-3.79(m,2h),2.82(t,j＝6.6hz,2h),2.14(d,j＝7.1hz,2h),1.79-1.70(m,2h),1.70-1.60(m,4h), 1.50-1.44(m,1h),1.39(t,j＝7.1hz,3h),1.22-1.07(m,3h),0.97-0.85(m,2h)；
13
c nmr(151mhz,cdcl3)δ 203.8(q,j＝4.1hz),166.2,138.9,129.92,129.88,126.2,124.6(q,j＝274.9hz),108.9,101.2(q,j＝33.5hz), 61.1,60.7,36.2,34.8,33.3,33.1(d,j＝10.4hz),26.2,26.0(d,j＝9.7hz),14.3；
19
f nmr(565mhz,cdcl3)δ
ꢀ‑
63.34；hrms:(esi)calcd for c
22h28
f3o
3
[m h]

397.1985；found 397.1990.
[0047]
实施例7
[0048][0049]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1g(49.5mg,0.24mmol)， 4-溴苯甲酸乙酯2a(45.8mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w, 390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物10(64.1mg,73％yield)。
[0050]1h nmr(600mhz,cdcl3)δ8.02(d,j＝8.4hz,2h),7.42(d,j＝8.3hz,2h),4.37(q,j＝7.1hz,2h), 3.69(s,3h),2.93-2.80(m,2h),2.60-2.51(m,2h),2.11(d,j＝7.1hz,2h),1.75-1.59(m,5h),1.49-1.41(m,1h), 1.39(t,j＝7.1hz,3h),1.24-1.06(m,3h),0.93-0.83(m,2h)；
13
c nmr(151mhz,cdcl3)δ203.3(q,j＝4.1 hz),172.9,166.3,139.1,130.0,126.2,123.7(q,j＝274.7hz),111.7,102.6(q,j＝33.6hz),61.2,51.9,36.4, 35.0,33.3,33.2,32.1,26.4,26.13,26.05,25.2,14.4；
19
f nmr(565mhz,cdcl3)δ-63.57；hrms:(esi)calcd for c
24h30
f3o
4
[m h]

439.2091；found 439.2096.
[0051]
实施例8
[0052][0053]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1h(52.8mg,0.2mmol)， 4-溴苯甲酸乙酯2a(55.0mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w, 390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物11(63.9mg,64％yield)。
[0054]1h nmr(400mhz,cdcl3)δ8.02(d,j＝8.5hz,2h),7.40(d,j＝8.5hz,2h),4.37(q,j＝7.1hz,2h), 3.74(d,j＝7.0hz,6h),3.59(t,j＝7.3hz,1h),3.23-3.11(m,2h),2.15-2.03(m,2h),1.72-1.56(m,5h),1.40(s, 1h),1.38(t,j＝7.1hz,3h),1.24-1.05(m,3h),0.95-0.80(m,2h)；
13
c nmr(151mhz,cdcl3)δ202.9(q,j＝ 4.1hz),168.94,168.85,166.2,138.6,130.2,130.1,126.3,122.6(q,274.4hz),110.0,102.9(q,j＝33.5hz), 61.2,53.0,50.1,36.3,35.0,33.23,33.17,29.3,26.3,26.09,25.99,14.4；
19
f nmr nmr(376mhz,cdcl3)δ
ꢀ‑
63.69；hrms:(esi)calcd for c
26h32
f3o
6
[m h]

497.2146；found 497.2155.
[0055]
实施例9
[0056][0057]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(76.4mg,0.24mmol)， 4-溴苯甲酸乙酯2a(45.8mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w, 390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物12(86.9mg,79％yield)。
[0058]1h nmr(400mhz,cdcl3)δ7.98(d,j＝8.5hz,2h),7.37(d,j＝8.6hz,2h),4.82(t,j＝1.7hz,1h), 4.69-4.61(m,1h),4.35(q,j＝7.1hz,2h),3.61(s,3h),3.47(s,3h),3.29-3.16(m,2h),2.76(s,2h),2.18-1.92 (m,2h),1.71-1.61(m,2h),1.61-1.59(m,3h),1.59-1.52(m,3h),1.42-1.33(m,4h),1.20-0.96(m,3h), 0.91-0.73(m,2h)；
13
c nmr(101mhz,cdcl3)δ204.3(q,j＝4.1hz),δ171.0,170.7,166.3,140.4,140.3, 130.0,129.8,126.7,123.1(q,j＝277.1hz),115.8,108.2,101.3(q,j＝33.5hz),61.2,56.5,52.6,52.5,39.4, 36.3,34.9,33.2,33.1,32.8,26.3,26.1,26.0,23.5,14.4；
19
f nmr(376mhz,cdcl3)δ-63.52；hrms:(esi) calcd for c
30h38
f3o
6
[m h]

551.2615；found 551.2623.
[0059]
实施例10
[0060][0061]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1j(48.8mg,0.2mmol)， 4-溴苯甲酸乙酯2a(55.0mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w, 390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物13(58.1mg,61％yield)。
[0062]1h nmr(600mhz,cdcl3)δ7.99(d,j＝8.4hz,2h),7.34(d,j＝8.4hz,2h),4.36(q,j＝7.1hz,2h), 3.15-2.95(m,2h),2.94-2.81(m,2h),2.64-2.48(m,2h),2.00-1.92(m,2h),1.65-1.57(m,2h),1.57-1.49(m, 3h),1.38(t,j＝7.1hz,3h),1.36-1.30(m,1h),1.26(s,3h),1.20-1.10(m,1h),1.09-0.96(m,2h),0.86-0.75(m, 2h)；
13
c nmr(151mhz,cdcl3)δ203.5(q,j＝4.1hz),214.6,214.2,166.2,139.0,130.3,129.9,126.5, 123.4(q,j＝274.9hz),109.3,102.8(q,j＝33.5hz),61.2,56.5,36.2,35.03,34.95,34.7,34.4,33.2,33.1,26.3, 26.1,25.9,23.6,14.4；
19
f nmr(565mhz,cdcl3)δ-63.98；hrms:(esi)calcd for c
27h32
f3o
4
[m h]
477.2247；found 477.2229.
[0063]
实施例11
[0064][0065]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1k(70.4mg,0.24mmol)， 4-溴苯甲酸乙酯2a(45.8mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w, 390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物14(73.5mg,70％yield)。
[0066]1h nmr(600mhz,cdcl3)δ8.01(d,j＝8.4hz,2h),7.85-7.80(m,2h),7.73-7.69(m,2h),7.44(d,j＝ 8.4hz,2h),4.36(q,j＝7.1hz,2h),3.94-3.81(m,2h),3.01-2.89(m,2h),2.10(d,j＝7.1hz,2h),1.76-1.68 (m,2h),1.67-1.56(m,3h),1.49-1.41(m,1h),1.39(t,j＝7.1hz,3h),1.22-1.06(m,3h),0.92-0.82(m,2h)；
13
c nmr(151mhz,cdcl3)δ204.0(q,j＝4.2hz),168.2,166.3,138.6,134.1,132.1,130.1,130.0,122.7(q,j＝ 274.4hz),126.4,123.4,109.0,101.2(q,j＝33.6hz),61.1,36.4,36.3,34.9,33.3,33.2,29.2,26.4,26.13,26.06, 14.4；
19
f nmr(565mhz,cdcl3)δ-63.45；hrms:(esi)calcd for c
30h31
f3no
4
[m h]

526.2200；found 526.2199.
[0067]
实施例12
[0068][0069]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(73.9mg,0.24mmol)， 4-溴苯甲酸乙酯2a(45.8mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w, 390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物15(83.1mg,73％yield,d.r.＝1/1)。
[0070]1h nmr(600mhz,cdcl3)δ8.02(d,j＝8.5hz,2h),7.42(d,j＝8.3hz,2h),4.74-4.67(m,1h),4.37(q, j＝7.1hz,2h),2.94-2.75(m,2h),2.57-2.45(m,2h),2.13(d,j＝7.1hz,2h),2.03-1.94(m,1h),1.88-1.79(m, 1h),1.76-1.59(m,7h),1.54-1.41(m,2h),1.39(t,j＝7.1hz,3h),1.37-1.33(m,1h),1.23-1.08(m,3h), 1.08-1.00(m,1h),1.00-0.94(m,1h),0.93-0.84(m,9h),0.75(dd,j＝6.9,3.5hz,3h)；
13
c nmr(151mhz, cdcl3)δ203.5(q,j＝4.2hz),172.1,172.0,166.3,139.2,130.02,130.00,126.3,123.77(q,j＝274.7hz), 123.76(q,j＝274.6hz),111.7,102.23(q,j＝33.6hz),102.21(q,j＝33.5hz),74.7,61.2,47.1,41.03,40.95, 36.5,36.4,35.03,34.98,34.3,33.3,33.23,33.22,32.73,32.69,
2.54(m,2h),2.14-2.01(m,2h),1.76-1.56(m,5h),1.53(d,j＝2.3hz,3h),1.46(s,3h),1.45-1.40(m,1h),1.40-1.35(m,6h),1.32(s,3h),1.22-1.14(m,1h),1.14-1.06(m,2h),0.93-0.82(m,2h)；
13
cnmr(151mhz,cdcl3)δ203.3(q,j＝4.0hz),171.8,166.2,138.9,130.04,130.01,129.6,126.2,123.7(q,j＝274.5hz),111.5,109.2,108.8,102.57(q,j＝33.5hz),102.56(q,j＝33.5hz),101.6,70.8,70.68,70.66,70.11,70.09,65.71,65.66,61.33,61.31,61.2,36.33,36.29,34.92,34.91,33.26,33.23,33.21,33.20,32.16,26.5,26.3,26.11,26.09,26.0,25.9,25.14,25.13,25.02,24.97,24.11,24.09,14.4；
19
fnmr(565mhz,cdcl3)δ-63.43,-63.44；hrms:(esi)calcdforc
35h46
f3o
9
[m h]

677.3448；found677.3453.
[0079]
实施例15
[0080][0081]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1o(138.9mg,0.24mmol)，4-溴苯甲酸乙酯2a(45.8mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物18(113.9mg,70％yield)。
[0082]1hnmr(600mhz,cdcl3)δ8.07-8.03(m,2h),7.50-7.43(m,2h),6.70-6.58(m,2h),4.39(q,j＝7.1hz,2h),3.05-2.88(m,2h),2.84-2.67(m,4h),2.18-2.15(m,2h),2.15(s,3h),1.85-1.78(m,1h),1.78-1.71(m,3h),1.71-1.64(m,2h),1.63-1.59(m,1h),1.59-1.50(m,3h),1.50-1.43(m,2h),1.42-1.38(m,4h),1.38-1.33(m,2h),1.33-1.28(m,3h),1.28-1.24(m,6h),1.24-1.12(m,7h),1.12-1.10(m,1h),1.09-1.02(m,3h),0.96-0.89(m,2h),0.88-0.84(m,12h)；
13
cnmr(151mhz,cdcl3)δ203.4(q,j＝4.2hz),171.7,166.3,139.1,130.1,127.5,126.3,123.7(q,j＝274.6hz),121.09,121.06,119.1,111.6,102.6(q,j＝33.4hz),76.3,61.2,40.2,39.5,37.6,37.5,37.4,36.4,35.0,33.3,33.0,32.8,32.5,31.0,28.1,26.4,26.12,26.06,25.3,24.9,24.6,24.3,22.9,22.8,22.6,21.1,19.9,19.8,16.3,14.5；
19
fnmr(565mhz,cdcl3)δ-63.31；hrms:(esi)calcdforc
50h72
f3o
5
[m h]

809.5326；found809.5341.
[0083]
实施例16
[0084][0085]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,
4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1p(83.8mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物19(43.9mg,52％yield)。
[0086]1h nmr(600mhz,cdcl3)δ7.66-7.62(m,1h),7.39-7.32(m,2h),7.31-7.27(m,1h),3.79(s,3h),3.78(s, 3h),3.63-3.54(m,2h),2.19-2.10(m,2h),1.88-1.75(m,2h),1.74-1.61(m,3h),1.53-1.42(m,1h),1.27-1.11 (m,3h),0.99-0.90(m,2h)；
13
c nmr(151mhz,cdcl3)δ197.6(q,j＝4.2hz),δ170.2,139.5,137.8,129.7, 129.1,127.4,123.6(q,j＝274.6hz),123.2,110.8,103.1(q,j＝33.7hz),63.8,53.5,53.4,37.4,36.1,35.1, 33.22,33.16,26.5,26.17,26.15；
19
f nmr(565mhz,cdcl3)δ-63.83；hrms:(esi)calcd for c
23h26
f3o
4
[m h]

423.1778；found 423.1782.
[0087]
实施例17
[0088][0089]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1q(91.7mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物20(31.4mg,34％yield)。
[0090]1h nmr(600mhz,cdcl3)δ7.73-7.70(m,1h),7.69-7.65(m,2h),7.31-7.28(m,1h),7.25(d,j＝8.2hz, 2h),7.13-7.09(m,1h),7.06-7.02(m,1h),4.64(d,j＝3.1hz,2h),2.38(s,3h),2.09(d,j＝7.0hz,2h), 1.70-1.60(m,5h),1.37-1.30(m,1h),1.17-1.09(m,3h),0.91-0.83(m,2h)；
13
c nmr(151mhz,cdcl3)δ195.2(q,j＝4.0hz),144.6,142.8,133.5,130.4,129.9,127.2,126.1,124.5,123.4,123.1(q,j＝275.0hz),115.4, 106.6,105.2,105.1(q,j＝33.8hz),51.6,35.8,35.0,33.02,32.91,26.3,26.01,25.91,21.6；
19
f nmr(565mhz, cdcl3)δ-63.99；hrms:(esi)calcd for c
25h27
f3no2s

[m h]

462.1709；found 462.1705.
[0091]
实施例18
[0092][0093]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(76.4mg,0.24 mmol)，溴苯2b(31.4mg,0.2mmol)，环己烷3a(168.0mg,2mmol)
和丙酮(0.5ml)。紫光灯(10w, 390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物21(67.0mg,70％yield)。
[0094]1h nmr(600mhz,cdcl3)δ7.32(d,j＝4.3hz,4h),7.28-7.24(m,1h),4.84(t,j＝1.7hz,1h), 4.71-4.66(m,1h),3.62(s,3h),3.45(s,3h),3.29-3.19(m,2h),2.79(d,j＝1.0hz,2h),2.13-2.06(m,1h), 2.03-1.96(m,1h),1.70-1.63(m,2h),1.63-1.61(m,3h),1.61-1.53(m,3h),1.44-1.35(m,1h),1.21-1.12(m, 1h),1.10-1.00(m,2h),0.89-0.77(m,2h)；
13
c nmr(151mhz,cdcl3)δ203.7(q,j＝4.2hz),171.1,170.7, 140.5,135.4,128.5,128.0,126.8,123.9(q,j＝274.4hz),115.6,108.5,100.4(q,j＝33.3hz),56.4,52.5,52.3, 39.2,36.3,34.8,33.13,33.05,32.9,26.3,26.1,25.9,23.5；
19
f nmr(565mhz,cdcl3)δ-63.68；hrms:(esi) calcd for c
27h34
f3o
4
[m h]

479.2404；found 479.2393.
[0095]
实施例19
[0096][0097]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴苯2c(44.9mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390 nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物22(57.9mg,57％yield)。
[0098]1h nmr(600mhz,cdcl3)δ7.24(d,j＝8.8hz,2h),6.85(d,j＝8.8hz,2h),4.83(t,j＝1.7hz,1h), 4.67(s,1h),3.79(s,3h),3.63(s,3h),3.51-3.45(m,3h),3.25-3.16(m,2h),2.78(s,2h),2.12-1.95(m,2h), 1.62(s,3h),1.60-1.53(m,2h),1.43-1.34(m,1h),1.21-1.11(m,1h),1.11-1.02(m,2h),0.91-0.77(m,2h)；
13
c nmr(151mhz,cdcl3)δ203.5(q,j＝4.2hz),δ171.3,170.9,159.5,140.6,128.1,127.5,124.0(q,j＝274.4 hz),115.6,114.0,108.1,100.4(q,j＝33.3hz),56.5,55.4,52.6,52.5,39.3,36.4,35.0,33.3,33.2,33.0,26.4, 26.2,26.0,23.6；
19
f nmr(565mhz,cdcl3)δ-63.69；hrms:(esi)calcd for c
28h36
f3o
5
[m h]

509.2509； found 509.2151.
[0099]
实施例20
[0100][0101]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴苯2d(55.9mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390 nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物23(71.0mg,64％yield)。
[0102]1h nmr(600mhz,cdcl3)δ7.62-7.56(m,4h),7.47-7.43(m,2h),7.42-7.39(m,2h),7.38-7.34(m,1h), 4.87(t,j＝1.7hz,1h),4.73-4.69(m,1h),3.66-3.62(m,3h),3.49(s,3h),3.28(d,j＝2.1hz,2h),2.82(s,2h), 2.17-2.00(m,2h),1.74-1.69(m,1h),1.68-1.65(m,1h),1.64(s,3h),1.62(s,1h),1.61-1.56(m,2h),1.48-1.38 (m,1h),1.22-1.14(m,1h),1.13-1.03(m,2h),0.94-0.80(m,2h)；
13
c nmr(151mhz,cdcl3)δ203.9(q,j＝ 4.2hz),171.2,170.9,140.8,140.6,140.4,134.4,129.0,127.7,127.3,127.2,127.1,124.0(q,j＝274.5hz),115.7, 108.3,100.8(q,j＝33.4hz),56.6,52.7,52.5,39.3,36.4,35.0,33.3,33.2,32.9,26.4,26.2,26.0,23.6；
19
f nmr (565mhz,cdcl3)δ-63.58；hrms:(esi)calcd for c
33h38
f3o
4
[m h]

555.2717；found 555.2726.
[0103]
实施例21
[0104][0105]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴苯2e(43.7mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390 nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物24(56.4mg,56％yield)。
[0106]1h nmr(600mhz,cdcl3)δ7.62(d,j＝8.6hz,2h),7.42(d,j＝8.7hz,2h),4.83(t,j＝1.6hz,1h), 4.65-4.62(m,1h),3.64(s,3h),3.51(s,3h),3.27-3.14(m,2h),2.76(s,2h),2.15-1.98(m,2h),1.67-1.61(m, 2h),1.60-1.59(m,3h),1.59-1.53(m,3h),1.40-1.31(m,1h),1.19-1.10(m,1h),1.09-0.98(m,2h),0.89-0.78 (m,2h)；
[0107]
13
c nmr(151mhz,cdcl3)δ204.4(q,j＝4.3hz),170.9,170.6,140.7,140.3,132.4,127.4,123.6(q,j＝274.7 hz),118.6,115.9,111.7,107.8,102.1(q,j＝33.7hz),56.4,52.8,52.6,39.4,36.3,34.9,33.2,33.2,32.5,26.3, 26.1,25.9,23.4；
19
f nmr(565mhz,cdcl3)δ-63.58；hrms:(esi)calcd for c
28h33
f3no
4
[m h]

504.2356； found 504.2354.
[0108]
实施例22
[0109][0110]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴苯2f(54.0mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390 nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物25(80.9mg,74％yield)。
[0111]1h nmr(600mhz,cdcl3)δ7.59(d,j＝8.2hz,2h),7.43(d,j＝8.1hz,2h),4.85(t,j
＝1.6hz,1h), 4.69-4.64(m,1h),3.64(s,3h),3.49(s,3h),3.30-3.19(m,2h),2.78(d,j＝1.1hz,2h),2.15-1.98(m,2h), 1.69-1.63(m,2h),1.62-1.61(m,3h),1.60-1.56(m,3h),1.43-1.35(m,1h),1.20-1.11(m,1h),1.11-1.00(m, 2h),0.90-0.79(m,2h)；
13
c nmr(151mhz,cdcl3)δ204.2(q,j＝4.2hz),171.0,170.8,140.5,139.6,130.2(q, j＝32.6hz),127.2,125.6(q,j＝3.7hz),124.1(q,j＝272.1hz),123.8(q,j＝274.5hz),115.9,107.9,101.6(q, j＝33.5hz),56.5,52.7,52.5,39.5,36.4,34.9,33.3,33.2,32.9,26.4,26.2,26.0,23.5；
19
f nmr(565mhz, cdcl3)δ-62.67,-63.65；hrms:(esi)calcd for c
28h33
f6o
4
[m h]

547.2278；found 547.2267.
[0112]
实施例23
[0113][0114]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴苯2g(47.6mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390 nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物26(42.7mg,41％yield)。
[0115]1h nmr(600mhz,cdcl3)δ7.92(d,j＝8.4hz,2h),7.41(d,j＝8.4hz,2h),4.83(s,1h),4.66(s,1h), 3.63(s,3h),3.49(s,3h),3.24(q,j＝15.7hz,2h),2.78(s,2h),2.59(s,3h),2.15-1.98(m,2h),1.65(d,j＝ 15.3hz,2h),1.60(s,3h),1.57(s,3h),1.44-1.33(m,1h),1.19-1.11(m,1h),1.11-0.99(m,2h),0.90-0.78(m, 2h)；
13
c nmr(151mhz,cdcl3)δ204.3(q,j＝4.0hz),δ197.5,170.9,170.7,140.5,140.3,136.4,128.7,126.9, 123.7(q,j＝274.6hz),115.7,108.0,101.4(q,j＝33.6hz),56.4,52.6,52.5,39.3,36.3,34.8,33.1,33.1,32.6, 26.7,26.2,26.1,25.9,23.4；
19
f nmr(565mhz,cdcl3)δ-63.60；hrms:(esi)calcd for c
29h36
f3o
5
[m h]
521.2509；found 521.2512.
[0116]
实施例24
[0117][0118]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴苯2h(67.9mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390 nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物27(54.4mg,45％yield)。
[0119]1h nmr(600mhz,cdcl3)δ7.75(d,j＝8.2hz,2h),7.32(d,j＝8.3hz,2h),4.82(t,j
＝1.7hz,1h), 4.68-4.63(m,1h),3.62(s,3h),3.49(s,3h),3.29-3.20(m,2h),2.78(s,2h),2.12-1.97(m,2h),1.71-1.65(m, 1h),1.64(s,3h),1.59-1.55(m,2h),1.43-1.36(m,1h),1.34(s,12h),1.33(s,2h),1.20-1.12(m,1h),1.11-1.04 (m,2h),0.90-0.79(m,2h)；
13
c nmr(151mhz,cdcl3)δ204.1(q,j＝4.1hz),171.2,170.9,140.6,138.4, 135.0,126.1,123.9(q,j＝274.5hz),115.7,108.7,100.9(q,j＝33.3hz),84.0,56.6,52.6,52.5,39.4,36.4,35.0, 33.3,33.2,32.9,26.4,26.2,26.1,25.00,24.98,23.6；
19
f nmr(565mhz,cdcl3)δ-63.65；hrms:(esi)calcd for c
33h45
bf3o
6
[m h]

605.3256；found 605.3253.
[0120]
实施例25
[0121][0122]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴苯2i(31.9mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390 nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物28(53.3mg,55％yield)。
[0123]1h nmr(600mhz,cdcl3)δ7.28-7.25(m,1h),7.24-7.20(m,1h),7.02-6.98(m,1h),4.85(t,j＝1.7hz, 1h),4.69-4.66(m,1h),3.65(s,3h),3.58(s,3h),3.20(s,2h),2.84-2.76(m,2h),2.14-2.01(m,2h),1.76-1.69 (m,2h),1.69-1.65(m,1h),1.63(s,3h),1.62-1.57(m,2h),1.48-1.40(m,1h),1.24-1.15(m,1h),1.15-1.08(m, 2h),0.95-0.85(m,2h)；
13
c nmr(151mhz,cdcl3)δ203.8(q,j＝4.1hz),171.2,170.9,140.6,136.3,126.7, 125.9,123.7(q,j＝274.6hz),121.6,115.8,104.2,101.1(q,j＝33.5hz),56.5,52.64,52.56,39.5,36.5,35.1, 33.33,33.29,33.1,26.4,26.2,26.1,23.6；
19
f nmr(565mhz,cdcl3)δ-63.72；hrms:(esi)calcd for c
25h32
f3o4s

[m h]

485.1968；found 485.1974.
[0124]
实施例26
[0125][0126]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴苯2j(31.9mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390 nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物29(37.6mg,39％yield)。
[0127]1h nmr(600mhz,cdcl3)δ8.62-8.56(m,1h),8.53-8.48(m,1h),7.65-7.59(m,1h),7.28-7.25(m,1h), 4.85(t,j＝1.6hz,1h),4.69-4.65(m,1h),3.64(s,3h),3.51(s,3h),3.27-3.17(m,2h),2.78(d,j＝1.0hz,2h), 2.14-1.98(m,2h),1.73(s,1h),1.65(d,j＝
11.6hz,2h),1.61(s,3h),1.58(d,j＝9.1hz,2h),1.43-1.34(m, 1h),1.18-1.10(m,1h),1.10-1.03(m,2h),0.89-0.79(m,2h)；
13
c nmr(151mhz,cdcl3)δ203.9(q,j＝4.1 hz),171.0,170.7,149.2,148.1,140.4,134.2,131.8,124.7(q,j＝274.8hz),123.4,115.9,106.0,101.6(q,j＝ 33.6hz),56.5,52.7,52.6,39.5,36.3,34.9,33.22,33.20,32.8,26.3,26.2,26.0,23.5；
19
f nmr(565mhz,cdcl3) δ-63.67；hrms:(esi)calcd for c
26h33
f3no
4
[m h]

480.2356；found 480.2355.
[0128]
实施例27
[0129][0130]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴苯2k(54.2mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390 nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物30(65.8mg,60％yield)。
[0131]1h nmr(600mhz,cdcl3)δ8.68(d,j＝2.2hz,1h),7.82-7.77(m,1h),7.68-7.63(m,1h),4.85(t,j＝1.6 hz,1h),4.68-4.63(m,1h),3.65(s,3h),3.53(s,3h),3.27-3.18(m,2h),2.78(d,j＝1.0hz,2h),2.15-2.02(m, 2h),1.68-1.61(m,3h),1.61(s,3h),1.57(d,j＝8.8hz,2h),1.43-1.35(m,1h),1.20-1.11(m,1h),1.11-1.02(m, 2h),0.90-0.80(m,2h)；
13
c nmr(151mhz,cdcl3)δ204.4(q,j＝4.1hz),170.8,170.6,148.4,147.5(q,j＝ 34.9hz),140.3,135.2,134.9,123.6(q,j＝274.7hz),121.5(q,j＝273.9hz),120.3(q,j＝2.6hz),116.0,105.3, 102.6(q,j＝33.7hz),56.4,52.8,52.7,39.7,36.3,35.0,33.3,33.2,32.7,26.3,26.1,25.9,23.4；
[0132]
19
f nmr(565mhz,cdcl3)δ-63.61,-67.94；hrms:(esi)calcd for c
27h32
f6no
4
[m h]

548.2230；found 548.2232.
[0133]
实施例28
[0134][0135]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴苯2l(45.1mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390 nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物31(39.6mg,39％yield)。
[0136]1h nmr(600mhz,cdcl3)δ8.16-8.12(m,1h),7.53-7.48(m,1h),6.74-6.69(m,1h),4.85(t,j＝1.6hz, 1h),4.70-4.65(m,1h),3.93(d,j＝0.9hz,3h),3.66(d,j＝0.7hz,3h),
4.70(m,1h),3.64(s,3h),3.46(s,3h),3.39 (s,2h),2.84(d,j＝1.1hz,2h),2.19-2.03(m,2h),1.78-1.71(m,1h),1.70-1.64(m,2h),1.62(s,3h),1.60-1.52 (m,2h),1.50-1.40(m,1h),1.23-1.13(m,1h),1.12-1.02(m,2h),0.94-0.80(m,2h)；
13
c nmr(151mhz, cdcl3)δ204.1(q,j＝4.1hz),171.2,170.9,140.6,139.3,135.3,131.9,127.2,125.7,124.7,124.0(q,j＝274.4 hz),123.0,122.9,121.8,119.6,115.7,108.6,100.8(q,j＝33.5hz),56.6,52.7,52.5,39.3,36.4,35.1,33.32, 33.25,33.2,26.4,26.2,26.0,23.7；
19
f nmr(565mhz,cdcl3)δ-63.46；hrms:(esi)calcd for c
33h36
f3o4s

[m h]

585.2281；found 585.2289.
[0145]
实施例31
[0146][0147]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴苯2o(77.3mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390 nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物34(74.7mg,58％yield)。
[0148]1h nmr(600mhz,cdcl3)δ8.18-8.14(m,1h),8.15-8.11(m,1h),7.66-7.59(m,2h),7.58-7.53(m,2h), 7.51-7.46(m,1h),7.45-7.41(m,2h),7.41-7.38(m,1h),7.38-7.35(m,1h),7.35-7.30(m,1h),4.87(t,j＝1.7 hz,1h),4.76-4.72(m,1h),3.66(s,3h),3.49(s,3h),3.43(s,2h),2.89-2.84(m,2h),2.19-2.04(m,2h), 1.79-1.73(m,1h),1.72-1.67(m,1h),1.66(s,3h),1.65-1.62(m,1h),1.61-1.55(m,2h),1.52-1.41(m,1h), 1.24-1.15(m,1h),1.13-1.06(m,2h),0.97-0.84(m,2h)；
13
c nmr(151mhz,cdcl3)δ203.8(q,j＝4.2hz), 171.3,171.0,141.2,140.7,140.6,137.4,130.0,127.6,127.0,126.9,125.5(q,j＝146.2hz),123.4,123.2,120.4, 120.3,118.3,115.5,110.0,109.8,109.0,100.3(q,j＝33.3hz),56.6,52.6,52.4,39.2,36.3,35.1,33.32,33.26, 33.2,26.3,26.1,26.0,23.6；
19
f nmr(565mhz,cdcl3)δ-63.54；hrms:(esi)calcd for c
39h41
f3no
4
[m h]
644.2982；found 644.2968.
[0149]
实施例32
[0150][0151]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴苯2p(59.3mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390 nm)照射下室温反应12小时，浓缩，快速柱层析，得
无色液体产物35(62.5mg,55％yield)。
[0152]1h nmr(600mhz,cdcl3)δ8.00-7.94(m,1h),7.93-7.89(m,1h),7.60-7.54(m,1h),7.54-7.50(m,1h), 7.50-7.45(m,1h),7.45-7.40(m,1h),7.39
–
7.33(m,1h),4.86(t,j＝1.6hz,1h),4.74-4.69(m,1h),3.64(s, 3h),3.46(s,3h),3.36(d,j＝2.4hz,2h),2.83(d,j＝1.0hz,2h),2.18-2.01(m,2h),1.75-1.64(m,2h),1.63(s, 3h),1.62-1.51(m,3h),1.49-1.40(m,1h),1.21-1.12(m,1h),1.12-1.02(m,2h),0.95-0.79(m,2h)；
13
c nmr (151mhz,cdcl3)δ203.9(q,j＝4.2hz),171.1,170.8,156.6,140.5,130.3,127.5,126.3,124.5,123.9(q,j＝ 274.5hz),123.0,120.8,118.7,115.5,111.8,111.6,108.6,100.5(q,j＝33.4hz),56.5,52.5,52.4,39.2,36.3, 34.9,33.5,33.2,33.1,26.3,26.1,25.9,23.6；
19
f nmr(565mhz,cdcl3)δ-63.59；hrms:(esi)calcd for c
33h36
f3o
5
[m h]

569.2509；found 569.2510.
[0153]
实施例33
[0154][0155]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴苯2q(41.1mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390 nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物35(66.2mg,62％yield)。
[0156]1h nmr(600mhz,cdcl3)δ7.87(d,j＝8.1hz,1h),7.51-7.46(m,1h),7.45-7.40(m,1h),5.31(s,2h), 4.84(t,j＝1.6hz,1h),4.68-4.63(m,1h),3.64(s,3h),3.51(s,3h),3.32-3.20(m,2h),2.78(s,2h),2.17-1.98 (m,2h),1.66-1.62(m,2h),1.60(s,3h),1.59-1.53(m,3h),1.43-1.33(m,1h),1.20-1.10(m,1h),1.09-0.97(m, 2h),0.91-0.78(m,2h)；
13
c nmr(151mhz,cdcl3)δ204.5(q,j＝4.2hz),170.9,170.7,170.6,147.2,142.4, 140.4,127.9,125.9,125.4,123.7(q,j＝274.8hz),120.3,115.9,108.2,101.9(q,j＝33.6hz),69.6,56.5,52.8, 52.6,39.5,36.4,34.9,33.24,33.17,33.1,26.3,26.1,26.0,23.5；
19
f nmr(565mhz,cdcl3)δ-63.56；hrms: (esi)calcd for c
29h34
f3o
6
[m h]

535.2302；found 535.2307.
[0157]
实施例34
[0158]
[0159]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(76.4mg,0.24 mmol)，芳基溴苯2r(88.6mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯 (10w,390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物37(79.5mg,52％yield,d.r. ＝1/1)。
[0160]1h nmr(600mhz,cdcl3)δ8.00-7.95(m,2h),7.43-7.37(m,2h),5.98-5.91(m,1h),5.48(d,j＝2.8hz, 1h),4.83(q,j＝1.5hz,1h),4.69-4.61(m,2h),4.38-4.28(m,2h),4.15-4.04(m,2h),3.64(d,j＝1.7hz,3h), 3.51(d,j＝6.3hz,3h),3.29-3.17(m,2h),2.81-2.74(m,2h),2.15-1.99(m,2h),1.67(s,1h),1.64(s,1h),1.60 (s,3h),1.59-1.56(m,2h),1.55(s,3h),1.40(s,3h),1.39-1.34(m,1h),1.31(s,3h),1.25(d,j＝2.7hz,3h), 1.18-1.09(m,1h),1.09-1.00(m,2h),0.90-0.79(m,2h)；
13
c nmr(151mhz,cdcl3)δ204.1(q,j＝7.2,4.0 hz),170.8,170.55,170.54,164.7,140.2,129.8,128.8,126.74,126.72,123.5(q,j＝274.4hz),115.7,115.6, 112.3,109.34,109.33,107.9,105.0,101.5(q,j＝33.3hz),101.4(q,j＝33.5hz),83.2,79.84,79.83,72.4,67.2, 56.3,52.5,52.4,39.24,39.21,36.14,36.10,34.7,33.02,33.00,33.0,32.49,32.46,26.77,26.76,26.6,26.12, 26.10,25.9,25.8,25.11,25.09,23.3；
19
f nmr(565mhz,cdcl3)δ-63.58,-63.60；
[0161]
实施例35
[0162][0163]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'
‑ꢀ
联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(76.4mg,0.24 mmol)，芳基溴苯2s(97.8mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯 (10w,390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物35(100.4mg,62％yield,d.r. ＝1/1)。
[0164]1h nmr(600mhz,cdcl3)δ7.47(t,j＝8.3hz,2h),7.42-7.35(m,2h),7.35-7.31(m,2h),7.31-7.27(m, 1h),7.24-7.19(m,1h),7.11-7.04(m,1h),7.02-6.92(m,1h),6.88-6.72(m,1h),6.05-4.91(m,1h),4.88-4.77 (m,1h),4.66(d,j＝10.5hz,1h),4.28-4.12(m,1h),3.68-3.60(m,3h),3.56-3.43(m,3h),3.30-3.16(m,2h), 2.86(s,2h),2.82-2.75(m,2h),2.70(s,1h),2.12-1.96(m,3h),1.93-1.86(m,1h),1.85-1.75(m,1h),1.68-1.48 (m,8h),1.44-1.30(m,1h),1.28-1.21(m,1h),1.18-0.97(m,3h),0.90-0.77(m,2h)；
13
c nmr(151mhz, cdcl3)δ203.86(q,j＝4.2hz),203.75(q,j＝4.0hz),172.3,172.0,170.98,170.96,170.95,170.71,170.67, 170.6,147.0,146.6,140.4,140.3,138.4,137.9,137.8,
烯炔化合物1i(63.7mg,0.2mmol)，烯基溴化合物2u(46.8mg,0.24mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w, 390nm)照射下室温反应12小时，浓缩，快速柱层析，得无色液体产物40(51.6mg,50％yield)。
[0172]1h nmr(600mhz,cdcl3)δ7.40-7.36(m,1h),7.36-7.32(m,1h),7.26-7.22(m,1h),7.20-7.15(m,1h), 6.93(d,j＝0.9hz,1h),4.87(t,j＝1.7hz,1h),4.71-4.68(m,1h),3.68(s,3h),3.64(s,3h),3.41-3.37(m,2h), 3.18(d,j＝3.1hz,2h),2.84-2.76(m,2h),2.19-2.03(m,2h),1.89-1.78(m,2h),1.75-1.68(m,2h),1.66(s,3h), 1.60(s,1h),1.54-1.45(m,1h),1.26-1.14(m,3h),1.03-0.93(m,2h)；
13
c nmr(151mhz,cdcl3)δ205.0(q,j ＝4.1hz),171.3,171.0,144.8,143.0,142.0,140.6,129.7,126.7,125.5,124.0(q,j＝275.0hz),123.8,121.2, 115.9,105.9,101.5(q,j＝33.3hz),56.5,52.69,52.65,39.8,39.7,36.7,35.2,33.6,33.4,31.9,26.4,26.2,26.1, 23.6；
19
f nmr(565mhz,cdcl3)δ-63.56；hrms:(esi)calcd for c
30h36
f3o
4
[m h]

517.2567；found 517.2562.
[0173]
实施例38
[0174][0175]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1a(47.1mg,0.24mmol)，苯甲酰氯2a’(28.1mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390nm) 照射在-5℃下反应8小时，浓缩，快速柱层析，得无色液体产物41(49.9mg,65％yield)。
[0176]1h nmr(600mhz,cdcl3)δ7.97-7.91(m,2h),7.61-7.57(m,1h),7.51-7.43(m,4h),7.43-7.37(m,2h), 7.38-7.32(m,1h),2.16(dd,j＝15.0,7.2hz,1h),2.09(dd,j＝15.0,7.2hz,1h),1.60-1.53(m,3h),1.54-1.44 (m,2h),1.43-1.34(m,1h),1.16-1.01(m,3h),0.84-0.72(m,2h)；
13
c nmr(151mhz,cdcl3)δ207.3(q,j＝ 4.2hz),191.8,137.4,133.6,131.4,129.4,128.8,128.7,128.4,127.9,123.1(q,j＝274.9hz),114.2,103.1(q,j ＝33.9hz),36.2,34.8,32.9,32.7,26.1,25.9,25.8；
19
f nmr(565mhz,cdcl3)δ-62.99；hrms:(esi)calcd for c
24h24
f3o

[m h]

385.1774；found 385.1777.
[0177]
实施例39
[0178][0179]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1a(47.1mg,0.24mmol)，酰氯2b’(43.3mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390nm) 照射在-5℃下反应8小时，浓缩，快速柱层析，得无色
1.47(m,2h),1.46-1.37(m,1h),1.17-1.03 (m,3h),0.84-0.74(m,2h)；
13
c nmr(151mhz,cdcl3)δ206.8(q,j＝4.1hz),190.2,166.0(d,j＝255.9hz), 133.7,133.6(d,j＝2.9hz),132.1(d,j＝9.4hz),131.18,128.9,128.8,127.8,124.0(q,j＝247.8hz),115.8, 115.6,114.0,103.4(q,j＝34.0hz),36.2,34.8,32.9,32.7,26.1,25.9,25.8；
19
f nmr(376mhz,cdcl3)δ-62.87,
ꢀ‑
103.72；hrms:(esi)calcd for c
24h23
f4o

[m h]

403.1679；found 403.1686.
[0189]
实施例42
[0190][0191]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1a(47.1mg,0.24mmol)，酰氯2e’(34.1mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390nm) 照射在-5℃下反应8小时，浓缩，快速柱层析，得无色液体产物45(49.7mg,60％yield)。
[0192]1h nmr(600mhz,cdcl3)δ7.56-7.52(m,1h),7.48-7.42(m,3h),7.42-7.33(m,4h),7.16-7.13(m,1h), 3.85(s,3h),2.20-2.07(m,2h),1.60-1.48(m,5h),1.47-1.37(m,1h),1.14-1.02(m,3h),0.85-0.75(m,2h)；
13
c nmr(151mhz,cdcl3)δ206.9(q,j＝4.2hz),191.6,159.7,138.7,131.5,129.5,128.9,128.8,127.9,123.2(q, j＝274.9hz),122.4,120.6,114.3,113.1,103.2(q,j＝33.9hz),55.4,36.3,34.9,32.9,32.8,26.2,26.0,25.9；
19
f nmr(565mhz,cdcl3)δ-62.95；hrms:(esi)calcd for c
25h26
f3o
2
[m h]

415.1879；found 415.1873.
[0193]
实施例43
[0194][0195]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1a(47.1mg,0.24mmol)，酰氯2f’(33.7mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390nm) 照射在-5℃下反应8小时，浓缩，快速柱层析，得无色液体产物46(50.3mg,61％yield)。
[0196]1h nmr(600mhz,cdcl3)δ7.56(s,2h),7.46(dd,j＝8.2,1.5hz,2h),7.40(dd,j＝8.4,6.7hz,2h), 7.37-7.33(m,1h),7.23(s,1h),2.36(s,6h),2.15(dd,j＝15.0,7.2hz,1h),2.07(dd,j＝15.0,7.1hz,1h), 1.60-1.51(m,3h),1.51-1.44(m,2h),1.44-1.34(m,1h),1.13-1.02(m,3h),0.83-0.71(m,2h)；
13
c nmr(151 mhz,cdcl3)δ207.7(q,j＝4.3hz),192.2,138.2,137.6,135.2,131.5,128.8,128.6,128.0,127.2,123.2(q,j＝ 274.7hz),
114.2,102.7(q,j＝33.8hz),36.3,34.8,32.9,32.6,26.1,25.9,25.8,21.1；
19
f nmr(565mhz, cdcl3)δ-63.03；hrms:(esi)calcd for c
26h28
f3o

[m h]

413.2087；found 413.2089.
[0197]
实施例44
[0198][0199]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1a(47.1mg,0.24mmol)，酰氯2g’(29.3mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390nm) 照射在-5℃下反应8小时，浓缩，快速柱层析，得无色液体产物45(36.7mg,47％yield)。
[0200]1h nmr(600mhz,cdcl3)δ7.82(dd,j＝3.9,1.2hz,1h),7.74(dd,j＝4.9,1.2hz,1h),7.46-7.41(m, 2h),7.41-7.37(m,2h),7.37-7.32(m,1h),7.16-7.12(m,1h),2.25-2.16(m,2h),1.67-1.55(m,5h),1.53-1.44 (m,1h),1.20-1.03(m,3h),0.90-0.79(m,2h)；
13
c nmr(151mhz,cdcl3)δ206.0(q,j＝4.1hz),182.8,143.4, 135.5,134.8,131.2,128.83,128.78,128.2,127.8,123.2(q,j＝274.8hz),114.2,103.5(q,j＝33.7hz),36.2, 35.0,33.0,32.8,26.2,25.9,25.8；
19
f nmr(565mhz,cdcl3)δ-63.15；hrms:(esi)calcd for c
22h22
f3os

[m h]

391.1338；found 391.1340.
[0201]
实施例45
[0202][0203]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1a(47.1mg,0.24mmol)，酰氯2h’(26.1mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390nm) 照射在-5℃下反应8小时，浓缩，快速柱层析，得无色液体产物45(32.2mg,43％yield)。
[0204]1h nmr(600mhz,cdcl3)δ7.69-7.66(m,1h),7.45-7.42(m,2h),7.40-7.37(m,2h),7.36-7.32(m,1h), 7.31-7.29(m,1h),6.58-6.56(m,1h),2.21(d,j＝7.2hz,2h),1.64-1.57(m,5h),1.52-1.45(m,1h),1.19-1.04 (m,3h),0.91-0.80(m,2h)；
13
c nmr(151mhz,cdcl3)δ207.4(q,j＝4.2hz),177.9,152.0,147.8,130.9, 128.77,128.76,127.9,123.2(q,j＝275.0hz),120.6,113.1,112.5,103.1(q,j＝33.9hz),36.1,34.9,33.0,32.8, 26.1,25.84,25.82；
19
f nmr(565mhz,cdcl3)δ-63.18；hrms:(esi)calcd for c
22h22
f3o
2
[m h]

375.1566； found 375.1568.
[0205]
实施例46
[0206][0207]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1k(70.4mg,0.24mmol)，酰氯2i’(30.9mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390nm)照射在-5℃下反应8小时，浓缩，快速柱层析，得无色液体产物45(70.3mg,71％yield)。
[0208]1hnmr(600mhz,cdcl3)δ7.86-7.81(m,2h),7.74-7.68(m,2h),7.59-7.54(m,2h),7.20-7.14(m,2h),3.96-3.86(m,2h),3.02-2.93(m,1h),2.82-2.73(m,1h),2.37(s,3h),1.88(dd,j＝14.7,7.2hz,1h),1.82(dd,j＝14.8,7.1hz,1h),1.55-1.43(m,3h),1.30-1.25(m,1h),1.20-1.11(m,2h),1.03-0.87(m,3h),0.63-0.47(m,2h)；
13
cnmr(151mhz,cdcl3)δ211.0(q,j＝4.2hz),192.3,168.2,143.3,135.0,133.9,132.0,128.7,128.7,123.1,122.8(q,j＝274.7hz),109.1,100.3(q,j＝33.9hz),36.0,36.0,34.7,32.6,32.4,28.4,26.0,25.84,25.77,21.6；
19
fnmr(565mhz,cdcl3)δ-63.22；hrms:(esi)calcdforc
29h29
f3no
3
[m h]

496.2094；found496.2094.
[0209]
实施例47
[0210][0211]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1k(70.4mg,0.24mmol)，酰氯2i’(30.9mg,0.2mmol)，四氢呋喃3b(144.2mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390nm)照射在-5℃下反应8小时，浓缩，快速柱层析，得无色液体产物45(74.4mg,77％yield,d.r＝1/1)。
[0212]1hnmr(600mhz,cdcl3)δ7.85-7.80(m,2h),7.73-7.66(m,2h),7.64-7.59(m,2h),7.20-7.16(m,2h),4.02-3.92(m,1h),3.92-3.84(m,1h),3.78-3.67(m,2h),3.60-3.54(m,1h),3.01-2.93(m,1h),2.85-2.76(m,1h),2.37(s,3h),2.35-2.27(m,1h),2.18-2.08(m,1h),1.76-1.62(m,3h),1.25-1.12(m,1h)；
13
cnmr(151mhz,cdcl3)δ211.0(q,j＝4.2hz),210.5(q,j＝4.1hz),191.8,168.1,143.5,134.7,133.9,132.0,128.9,128.7,123.1,122.7(q,j＝274.5hz),122.7(q,j＝274.2hz),110.0,109.4,99.3(q,j＝34.6hz),99.0(q,j＝34.6hz),76.1,76.0,67.7,67.6,35.8,32.9,32.5,30.7,30.6,28.31,28.28,25.3,21.6；
19
fnmr(565mhz,cdcl3)δ-63.40,-63.70；hrms:(esi)calcdforc
27h25
f3no
4
[m h]

484.1730；found484.1728.
[0213]
实施例48
[0214][0215]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(4.9mg,0.01mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1k((117.2mg,0.4mmol)，炔基溴化物2a”(52.3mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(6w,390nm)照射在-5℃下反应6小时，浓缩，快速柱层析，得无色液体产物51(81.4mg,73％yield)。
[0216]1hnmr(600mhz,cdcl3)δ7.84(dd,j＝5.4,3.0hz,2h),7.71(dd,j＝5.5,3.0hz,2h),3.97-3.81(m,2h),2.68-2.53(m,2h),2.03-1.90(m,2h),1.79-1.72(m,1h),1.69-1.59(m,4h),1.42-1.34(m,1h),1.25-1.12(m,3h),1.06(d,j＝3.3hz,21h),0.89-0.78(m,2h)；
13
cnmr(151mhz,cdcl3)δ209.2(q,j＝4.1hz),167.9,133.9,132.0,123.2,122.9(q,j＝274.7hz),98.8(q,j＝33.8hz),98.4,96.9,94.1,36.2,35.9,34.5,32.83,32.81,32.3,26.4,26.00,25.98,18.50,11.1；
19
fnmr(565mhz,cdcl3)δ-63.97；hrms:(esi)calcdforc
32h43
f3no2si

[m h]

558.3009；found558.3005.
[0217]
实施例49
[0218][0219]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(4.9mg,0.01mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1k((117.2mg,0.4mmol)，炔基溴化物2b”(35.0mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(6w,390nm)照射在-5℃下反应6小时，浓缩，快速柱层析，得无色液体产物52(52.1mg,55％yield)。
[0220]1hnmr(600mhz,cdcl3)δ7.84(dd,j＝5.4,3.0hz,2h),7.71(dd,j＝5.5,3.0hz,2h),3.97-3.83(m,2h),2.67-2.54(m,2h),1.99(d,j＝7.2hz,2h),1.80-1.59(m,5h),1.44-1.34(m,1h),1.23-1.08(m,3h),0.90-0.78(m,2h),0.13(s,9h)；
13
cnmr(151mhz,cdcl3)δ209.4(q,j＝4.1hz),168.3,134.3,132.4,123.6,123.2(q,j＝274.6hz),100.7,99.4(q,j＝33.9hz),96.9,94.4,36.6,36.2,34.9,33.20,33.17,32.4,26.7,26.4,26.3,0.0；
19
fnmr(565mhz,cdcl3)δ-63.97；hrms:(esi)calcdforc
26h31
f3no2si

[m h]

474.2071；found474.2066.
[0221]
实施例50
[0222][0223]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(4.9mg,0.01mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1k((117.2mg,0.4mmol)，炔基溴化物2c”(36.2mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(6w,390nm)照射在-5℃下反应6小时，浓缩，快速柱层析，得无色液体产物53(48.7mg,51％yield)。
[0224]1hnmr(600mhz,cdcl3)δ7.84-7.80(m,2h),7.69-7.66(m,2h),7.39-7.35(m,2h),7.31-7.26(m,3h),4.06-3.92(m,2h),2.78-2.63(m,2h),2.02(d,j＝7.2hz,2h),1.83-1.63(m,5h),1.48-1.39(m,1h),1.26-1.18(m,2h),1.16-1.09(m,1h),0.91-0.82(m,2h)；
13
cnmr(151mhz,cdcl3)δ208.7(q,j＝4.2hz),168.1,134.0,132.1,131.6,128.6,128.3,123.3,122.9(q,j＝274.7hz),122.6,99.0(q,j＝33.8hz),94.4,94.2,81.6,36.4,35.9,34.6,33.0,32.9,32.4,26.4,26.04,26.00；
19
fnmr(565mhz,cdcl3)δ-63.97；hrms:(esi)calcdforc
29h27
f3no
2
[m h]

478.1988；found478.1984.
[0225]
实施例51
[0226][0227]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(4.9mg,0.01mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1k((117.2mg,0.4mmol)，炔基溴化物2d”(42.2mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(6w,390nm)照射在-5℃下反应6小时，浓缩，快速柱层析，得无色液体产物54(40.6mg,40％yield)。
[0228]1hnmr(600mhz,cdcl3)δ7.84-7.80(m,2h),7.69-7.67(m,2h),7.32-7.28(m,2h),6.83-6.78(m,2h),4.08-3.88(m,1h),3.81(s,3h),2.76-2.60(m,2h),2.07-1.96(m,2h),1.84-1.61(m,5h),1.50-1.37(m,1h),1.30-1.18(m,3h),0.90-0.78(m,2h)；
13
cnmr(151mhz,cdcl3)δ208.5(q,j＝4.1hz),168.1,159.8,133.9,133.04,132.03,123.2,122.9(q,j＝274.7hz),114.7,113.8,98.7(q,j＝33.9hz),94.5,94.3,80.2,55.3,36.4,35.8,34.5,32.90,32.87,32.4,26.34,25.99,26.0；
19
fnmr(565mhz,cdcl3)δ-63.87；hrms:(esi)calcdforc
30h29
f3no
3
[m h]

508.2094；found508.2091.
[0229]
实施例52
[0230][0231]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(4.9mg,0.01mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1k((117.2mg,0.4mmol)，炔基溴化物2e”(63.4mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(6w,390nm)照射在-5℃下反应6小时，浓缩，快速柱层析，得无色液体产物54(74.8mg,61％yield)。
[0232]1hnmr(600mhz,cdcl3)δ7.84(dd,j＝5.4,3.0hz,2h),7.71(dd,j＝5.4,3.0hz,2h),3.95-3.84(m,2h),2.65-2.54(m,2h),1.97(d,j＝7.1hz,2h),1.79-1.71(m,3h),1.69-1.54(m,8h),1.50-1.43(m,2h),1.44-1.35(m,2h),1.32-1.25(m,1h),1.22-1.06(m,3h),0.90-0.79(m,11h),0.12(s,3h),0.12(s,3h)；
13
cnmr(151mhz,cdcl3)δ208.5(q,j＝4.2hz),167.9,133.9,132.0,123.2,122.9(q,j＝274.7hz),99.2,99.0(q,j＝33.9hz),93.7,69.5,40.84,40.79,36.2,35.9,34.5,32.92,32.87,32.1,26.3,26.0,25.8,25.2,22.7,18.1,-3.08,-3.09；
19
fnmr(565mhz,cdcl3)δ-64.10；hrms:(esi)calcdforc
35h47
f3no3si

[m h]

614.3272；found614.3268.
[0233]
实施例53
[0234][0235]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(4.9mg,0.01mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1k((117.2mg,0.4mmol)，炔基溴化物2f”(80.2mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(6w,390nm)照射在-5℃下反应6小时，浓缩，快速柱层析，得无色液体产物56(97.6mg,70％yield)。
[0236]1hnmr(600mhz,cdcl3)δ7.88-7.86(m,2h),7.73-7.71(m,2h),7.64-7.58(m,4h),7.34-7.28(m,4h),7.25-7.20(m,2h),3.98-3.90(m,2h),2.73-2.65(m,2h),2.00(d,j＝7.1hz,2h),1.76-1.63(m,5h),1.44-1.37(m,1h),1.21-1.08(m,3h),0.98(s,9h),0.88-0.81(m,2h),0.02(s,3h),-0.00(s,3h)；
13
cnmr(151mhz,cdcl3)δ208.6(q,j＝4.1hz),167.9,146.38,146.35,134.0,132.0,128.0,127.9,127.1,126.00,125.97,123.2,122.8(q,j＝274.8hz),99.6(q,j＝34.1hz),97.0,93.5,80.7,75.9,36.0,35.8,34.5,32.90,32.86,32.1,26.3,26.0,25.91,25.90,18.4,-3.46,-3.48；
19
fnmr(565mhz,cdcl3)δ-63.97；hrms:(esi)calcdforc
42h46
f3no3sina

[m na]

720.3091；found720.3084.
[0237]
实施例54
[0238][0239]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(4.9mg,0.01mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1k((117.2mg,0.4mmol)，炔基溴化物2g”(45.8mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(6w,390 nm)照射在-5℃下反应6小时，浓缩，快速柱层析，得无色液体产物57(49.4mg,47％yield)。
[0240]1h nmr(600mhz,cdcl3)δ7.86-7.78(m,2h),7.74-7.67(m,2h),3.89-3.80(m,1h),3.82-3.74(m,1h), 2.93-2.78(m,4h),2.56(s,2h),2.54-2.41(m,2h),1.95-1.86(m,2h),1.70-1.56(m,5h),1.35-1.26(m,1h), 1.20-1.03(m,6h),0.84-0.70(m,2h)；
13
c nmr(151mhz,cdcl3)δ215.37,215.35,208.7(q,j＝4.2hz),167.9, 133.9,131.9,123.2,122.7(q,j＝274.7hz),98.8(q,j＝33.8hz),93.2,89.5,75.0,55.2,35.9,35.74,35.72, 35.71,34.4,32.9,32.8,32.4,26.2,25.89,25.86,25.4,19.2；
19
f nmr(565mhz,cdcl3)δ-64.03；hrms:(esi) calcd for c
30h31
f3no
4
[m h]

526.2199；found 526.2194.
[0241]
实施例55
[0242][0243]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(4.9mg,0.01mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1k((117.2mg,0.4mmol)，炔基溴化物2h”(126.0mg,0.2mmol)，环己烷3a(168.0mg,2mmol)和丙酮(0.5ml)。紫光灯(6w,390 nm)照射在-5℃下反应6小时，浓缩，快速柱层析，得无色液体产物58(93.5mg,52％yield,d.r.＝1/1)。
[0244]1h nmr(600mhz,cdcl3)δ7.86-7.81(m,2h),7.74-7.68(m,2h),7.18-7.13(m,1h),6.63-6.59(m,1h), 6.58-6.53(m,1h),3.96-3.83(m,2h),2.88-2.73(m,2h),2.69-2.56(m,2h),2.39-2.17(m,3h),1.98(d,j＝7.1 hz,3h),1.91-1.59(m,11h),1.50-1.35(m,5h),1.25-1.07(m,3h),0.98(s,9h),0.88(s,9h),0.87-0.86(m,3h), 0.85-0.82(m,1h),0.189(s,3h),0.187(s,3h),0.16-0.11(m,6h)；
13
c nmr(151mhz,cdcl3)δ208.5(q,j＝ 3.9hz),208.3(q,j＝4.3hz),167.9,167.8,153.2,137.93,137.89,133.9,133.29,133.26,132.0,126.23,126.19, 123.2,122.8(q,j＝274.8hz),119.9,117.1,117.0,99.24,99.17,99.07(q,j＝34.2hz),99.06(q,j＝33.9hz), 93.9,93.8,81.08,81.05,78.6,78.5,48.7,48.6,
48.5,43.7,43.6,40.3,40.2,39.5,39.4,36.02,36.01,35.9,35.8, 34.5,33.07,33.05,32.97,32.92,32.89,32.86,32.21,32.15,29.7,27.3,26.5,26.4,26.33,26.31,26.00,25.97, 25.8,25.7,23.1,18.2,18.1,13.21,13.19,-3.16,-3.17,-3.3,-4.4；
19
f nmr(565mhz,cdcl3)δ-64.05,-64.06； hrms:(esi)calcd for c
53h72
f3no4si2na

[m na]

922.4844；found 922.4830.
[0245]
实施例56
[0246][0247]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴化物2a(55.0mg,0.24mmol)，四氢呋喃3b(144.2mg,2mmol)和丙酮(0.5ml)。紫光灯(10w, 390nm)照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物59(67.8mg,63％yield,d.r.＝1/1)。
[0248]1h nmr(600mhz,cdcl3)δ8.00(dd,j＝8.6,2.4hz,2h),7.46(dd,j＝8.3,5.8hz,2h),4.84-4.79(m, 1h),4.68-4.63(m,1h),4.36(q,j＝7.1hz,2h),3.98-3.90(m,1h),3.82-3.75(m,1h),3.69-3.63(m,1h),3.62 (d,j＝5.5hz,3h),3.50(d,j＝6.4hz,3h),3.29-3.21(m,2h),2.78(s,2h),2.54-2.42(m,1h),2.39-2.23(m, 1h),1.94-1.77(m,3h),1.63-1.58(m,3h),1.45-1.36(m,1h),1.38(t,j＝7.1hz,3h)；
13
c nmr(151mhz, cdcl3)δ204.8(q,j＝4.0hz),204.7(q,j＝3.7hz),170.89,170.85,170.66,170.63,166.1,140.23,140.22, 139.8,139.7,129.9,129.7,126.64,126.60,123.41(q,j＝274.5hz),123.39(d,j＝274.5hz),115.9,108.4, 108.3,99.85(q,j＝34.2hz).99.83(q,j＝34.3hz),76.6,76.4,67.69,67.68,61.0,56.4,56.3,52.6,52.5,52.4, 39.4,39.3,33.2,32.9,32.4,32.3,31.3,31.0,25.48,25.45,23.3,14.3；
19
f nmr(565mhz,cdcl3)δ-63.71,
ꢀ‑
63.77；hrms:(esi)calcd for c
28h34
f3o
7
[m h]

539.2251；found 539.2252.
[0249]
实施例57
[0250][0251]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴化物2a(55.0mg,0.24mmol)，环戊烷3c(140.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390 nm)照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物60(76.1mg,71％yield)。
[0252]1h nmr(600mhz,cdcl3)δ8.02-7.98(m,2h),7.42-7.36(m,2h),4.85-4.81(m,1h),4.67-4.64(m,1h), 4.37(q,j＝7.1hz,2h),3.63(s,3h),3.47(s,3h),3.28(d,j＝15.6hz,1h),3.21(d,j＝15.6hz,1h),2.78(s, 2h),2.23(dd,j＝15.3,6.8hz,1h),2.13(dd,j＝15.3,8.0hz,1h),1.97-1.89(m,1h),1.74-1.66(m,1h),1.61 (s,3h),1.58-1.48(m,3h),1.47-1.40(m,2h),1.39(t,j＝7.1hz,3h),1.11-1.05(m,1h),1.04-0.96(m,1h)；
13
c nmr(151mhz,cdcl3)δ204.4(q,j＝4.2hz),170.9,170.6,166.1,140.3,140.0,129.9,129.7,126.6,123.7 (q,j＝274.7hz),115.7,108.2,102.5(q,j＝33.4hz),61.0,56.4,52.5,52.3,39.3,37.6,33.5,32.6,32.53,32.50, 25.2,23.4,14.3；
19
f nmr(565mhz,cdcl3)δ-63.64；hrms:(esi)calcd for c
29h36
f3o
6
[m h]

537.2459； found 537.2459.
[0253]
实施例58
[0254][0255]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴化物2a(55.0mg,0.24mmol)，环辛烷3d(244.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10w,390 nm)照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物61(89.1mg,77％yield)。
[0256]1h nmr(600mhz,cdcl3)δ7.99(d,j＝8.6hz,2h),7.38(d,j＝8.6hz,2h),4.86-4.81(m,1h), 4.68-4.64(m,1h),4.36(q,j＝7.1hz,2h),3.63(s,3h),3.47(s,3h),3.29(d,j＝15.6hz,1h),3.21(d,j＝15.6 hz,1h),2.78(d,j＝1.0hz,2h),2.11(dd,j＝15.3,6.5hz,1h),2.02(dd,j＝15.2,7.9hz,1h),1.67-1.62(m, 1h),1.60(s,3h),1.57-1.41(m,7h),1.40-1.28(m,7h),1.27-1.11(m,3h)；
13
c nmr(151mhz,cdcl3)δ204.4 (q,j＝4.1hz),170.9,170.6,166.1,140.3,140.2,129.9,129.7,126.6,123.7(q,j＝274.7hz),115.6,108.2, 101.8(q,j＝33.2hz),61.0,56.4,52.5,52.3,39.3,35.66,35.60,32.6,32.4,32.1,26.85,26.77,26.2,25.2,25.1, 23.4,14.3；
19
f nmr(565mhz,cdcl3)δ-63.54；hrms:(esi)calcd for c
32h42
f3o
6
[m h]

579.2928；found 579.2937.
[0257]
实施例59
[0258][0259]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴化物2a(55.0mg,0.24mmol)，碳氢键化合物3e
(274.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10 w,390nm)照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物62(72.5mg,60％yield,d.r.＝ 1.8/1)。
[0260]1h nmr(600mhz,cdcl3)δ8.02(dd,j＝8.5,1.5hz,2h),7.40(dd,j＝8.5,2.7hz,2h),4.88-4.82(m, 1h),4.69-4.65(m,1h),4.38(q,j＝7.1hz,2h),3.64(d,j＝4.5hz,3h),3.48(d,j＝9.0hz,3h),3.43-3.38(m, 0.4h),3.35-3.28(m,2h),3.26-3.16(m,1.8h),2.82-2.76(m,2h),2.29-2.21(m,0.4h),2.18-2.09(m,1.2h), 2.05-1.96(m,0.4h),1.94-1.86(m,0.4h),1.86-1.71(m,1.6h),1.64-1.59(m,3h),1.59-1.50(m,0.7h),1.40(t,j＝ 7.1hz,3h),1.31-1.13(m,0.3h),0.86(d,j＝6.5hz,2h),0.81(d,j＝6.5hz,1h)；
13
c nmr(151mhz,cdcl3) δ204.4(q,j＝4.1hz,major),204.3(q,j＝4.1hz,minor),171.0,170.9,170.7,170.6,166.1,140.3,139.9,139.8, 130.2,130.1,129.9,129.1,126.79,126.75,123.6(q,j＝274.9hz),115.9,115.81,115.79,108.9,108.8,100.9(q, j＝33.6hz,major).100.8(q,j＝33.7hz,minor),61.1,56.44,56.40,52.65,52.63,52.46,52.43,39.6,39.4,39.3, 39.0,34.4,34.1,32.9,32.8,30.98,30.93,30.42,30.38,23.43,23.41,18.8,18.7,14.3；
19
f nmr(565mhz,cdcl3) δ-63.53(major),-63.72(minor)；hrms:(esi)calcd for c
28h35
brf3o
6
[m h]

603.1564；found 603.1575.
[0261]
实施例60
[0262][0263]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴化物2a(55.0mg,0.24mmol)，碳氢键化合物3f(172.4mg,2mmol)和丙酮(0.5ml)。紫光灯(10 w,390nm)照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物63(45.3mg,41％yield)。
[0264]1h nmr(600mhz,cdcl3)δ8.03-7.97(m,2h),7.40-7.35(m,2h),4.86-4.81(m,1h),4.69-4.65(m,1h), 4.36(q,j＝7.1hz,2h),3.65(s,3h),3.38(s,3h),3.29(d,j＝15.3hz,1h),3.22(d,j＝15.3hz,1h),2.82-2.73 (m,2h),2.18(d,j＝15.0hz,1h),2.02(d,j＝15.0hz,1h),1.61(t,j＝1.1hz,3h),1.42-1.36(m,1h),1.39(t, j＝7.1hz,3h),0.75(m,3h),0.74(d,j＝6.8hz,3h),0.73(d,j＝6.8hz,3h),0.67(s,3h)；
13
c nmr(151 mhz,cdcl3)δ206.31(q,j＝3.8hz),171.0,170.6,166.2,140.4,140.3,129.9,129.7,126.8,126.5,123.9(q,j＝ 274.8hz),115.5,107.4,99.43(q,j＝33.3hz),61.08,61.05,56.5,52.6,52.3,39.3,36.5,36.3,35.7,32.7,23.78, 23.75,23.5,17.34,17.27,14.3；
19
f nmr(565mhz,cdcl3)δ-62.87；hrms:(esi)calcd for c
30h40
f3o
6
[m h]

553.2772；found 553.2779.
[0265]
实施例61
[0266][0267]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴化物2a(55.0mg,0.24mmol)，碳氢键化合物3g(272.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10 w,390nm)照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物64(39.8mg,33％yield,5/4r.r.)。
[0268]1h nmr(600mhz,cdcl3)δ8.04-7.93(m,2h),7.44-7.33(m,2h),4.86-4.80(m,1h),4.69-4.64(m,1h), 4.30-4.32(m,2h),3.66(s,1.6h),3.63(s,1.4h),3.48(s,1.4h),3.43(s,1.6h),3.32-3.19(m,2h),2.78(d,j＝1.8 hz,2h),2.33(d,j＝7.6hz,0.8h),2.03(d,j＝14.7hz,0.6h),1.85(d,j＝14.7hz,0.6h),1.82-1.65(m,6h), 1.63-1.59(m,3h),1.59-1.46(m,3h),1.45-1.34(m,9h)；
13
c nmr(151mhz,cdcl3)δ206.0(q,j＝3.9hz), 204.1(q,j＝4.1hz),170.99,170.91,170.60,170.56,166.2,140.45,140.35,140.3,140.1,129.9,129.8,129.7, 129.6,126.8,126.5,123.8(q,j＝274.6hz),123.7(q,j＝274.7hz),115.7,115.6,108.4,107.1,101.7(q,j＝ 33.7hz),98.7(q,j＝33.7hz),61.1,56.4,56.3,52.6,52.5,52.4,52.3,42.5,42.0,40.7,39.24,39.20,38.9,38.7, 38.1,36.6,33.8,32.6,32.5,31.8,31.3,31.2,31.0,30.3,28.4,27.8,27.7,23.5,23.4,14.3；
19
f nmr(565mhz, cdcl3)δ-63.04,-63.64；hrms:(esi)calcd for c
34h42
f3o
6
[m h]

603.2928；found 603.2912.
[0269]
实施例62
[0270][0271]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴化物2a(55.0mg,0.24mmol)，碳氢键化合物3h(244.2mg,2mmol)和丙酮(0.5ml)。紫光灯(10 w,390nm)照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物65(48.2mg,41％yield)。
[0272]1h nmr(600mhz,cdcl3)δ8.01-7.95(m,2h),7.42-7.36(m,2h),6.78-6.73(m,2h),6.71-6.66(m,1h), 6.62-6.56(m,1h),6.28-6.21(m,1h),4.85-4.82(m,1h),4.68-4.65(m,1h),4.38(q,j＝7.1hz,2h),3.61(s,3h), 3.49(s,3h),3.26-3.15(m,2h),2.93-2.75(m,4h),1.61(s,3h),1.40(t,j＝7.1hz,3h)；
13
c nmr(151mhz, cdcl3)δ205.5(q,j＝4.0hz),170.9,170.7,166.2,147.02,147.95,140.2,139.1,130.1,129.7,126.7,123.2(q,j ＝
274.3hz),121.7,116.0,109.2,108.7,108.6,108.4,95.9(q,j＝35.3hz),61.1,56.4,52.6,52.4,39.8,32.5, 32.2,23.4,14.3；
19
f nmr(565mhz,cdcl3)δ-63.78；hrms:(esi)calcd for c
31h32
f3o
8
[m h]

589.2044； found 589.2030.
[0273]
实施例63
[0274][0275]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴化物2a(55.0mg,0.24mmol)，碳氢键化合物3i(176.2mg,2mmol)和丙酮(0.5ml)。紫光灯(10 w,390nm)照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物66(76.5mg,69％yield,d.r.＝ 1/1)。
[0276]1h nmr(600mhz,cdcl3)δ8.02-7.97(m,2h),7.48-7.44(m,2h),4.86-4.81(m,1h),4.68-4.64(m,1h), 4.39-4.34(m,2h),3.71-3.55(m,8h),3.53-3.45(m,4h),3.29-3.22(m,3h),2.83-2.74(m,2h),2.40-2.16(m, 2h),1.64-1.58(m,3h),1.41-1.33(m,3h)；
13
c nmr(151mhz,cdcl3)δ205.0(q,j＝4.0hz),204.6(q,j＝4.0 hz),170.9,170.7,166.1,140.22,140.18,139.6,139.5,130.1,129.74,129.73,126.7,126.6,123.4(q,j＝274.6 hz),123.3(q,j＝274.3hz),116.0,115.9,109.2,108.5,99.0(q,j＝34.5hz),98.3(q,j＝34.2hz),72.89,72.85, 70.7,70.5,66.54,66.47,66.33,66.24,61.1,56.43,56.40,52.6,52.4,39.7,39.5,32.4,32.3,29.5,29.0,23.4,14.3；
19
f nmr(565mhz,cdcl3)δ-63.70,-64.05；hrms:(esi)calcd for c
28h34
f3o
8
[m h]

555.2200；found 555.2207.
[0277]
实施例64
[0278][0279]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴化物2a(55.0mg,0.24mmol)，碳氢键化合物3j(330.1mg,2mmol)和丙酮(0.5ml)。紫光灯(10 w,390nm)照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物67(70.6mg,56％yield,d.r.＝ 1.2/1)。
[0280]
major diastereoisomer:1h nmr(600mhz,cdcl3)δ8.02-7.97(m,2h),7.46(d,j＝8.5hz,2h), 4.84-4.81(m,1h),4.66(d,j＝1.7hz,1h),4.61-4.57(m,1h),4.37(q,j＝7.1hz,2h),3.93-3.83(m,2h), 3.78-3.72(m,1h),3.63(s,3h),3.50(s,3h),3.26(q,j＝15.6hz,2h),2.81-2.76(m,2h),2.46(dd,j＝15.3,7.6 hz,1h),2.23(dd,j＝15.3,5.5hz,
1h),2.07-2.00(m,1h),1.91-1.81(m,2h),1.73-1.67(m,1h),1.60(s,3h), 1.39(t,j＝7.1hz,3h)；
13
c nmr(151mhz,cdcl3)δ204.8(q,j＝3.9hz),170.9,170.7,166.2,140.21,140.37, 139.7,129.9,129.7,126.8,126.6,123.4(q,j＝274.6hz),115.9,108.5,98.7(q,j＝34.2hz),70.0,62.9,61.1, 56.3,52.6,52.4,49.4,39.4,39.3,33.8,33.1,32.3,23.4,14.3；
19
f nmr(565mhz,cdcl3)δ-63.78；
[0281]
minor diastereoisomer:1h nmr(600mhz,cdcl3)δ8.03-7.97(m,2h),7.49(d,j＝8.4hz,2h), 4.86-4.82(m,1h),4.68-4.64(m,2h),4.37(q,j＝7.1hz,2h),3.96-3.90(m,1h),3.73-3.64(m,2h),3.64(s,3h), 3.50(s,3h),3.28(s,2h),2.84-2.77(m,2h),2.39-2.30(m,2h),2.04-1.96(m,2h),1.83-1.77(m,2h),1.62(s, 3h),1.39(t,j＝7.1hz,3h)；
13
c nmr(151mhz,cdcl3)δ204.5(q,j＝3.9hz),171.0,170.7,166.2,140.2, 139.6,129.9,129.7,126.6,123.38(q,j＝274.2hz),116.0,109.1,99.54(q,j＝34.3hz),69.8,62.8,61.1,56.4, 52.7,52.5,49.6,39.6,39.5,33.8,32.7,32.3,23.4,14.3；
19
f nmr(565mhz,cdcl3)δ-64.14；
[0282]
hrms:(esi)calcd for c
29h35
brf3o
7
[m h]

631.1513；found 631.1521.
[0283]
实施例65
[0284][0285]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴化物2a(55.0mg,0.24mmol)，碳氢键化合物3k(176.4mg,2mmol)和丙酮(0.5ml)。紫光灯(10 w,390nm)照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物68(34.4mg,31％yield)。
[0286]1h nmr(600mhz,cdcl3)δ8.01-7.97(m,2h),7.48-7.43(m,2h),4.84-4.81(m,1h),4.67-4.64(m,1h), 4.37(q,j＝7.1hz,2h),3.62(s,3h),3.53(s,3h),3.50-3.44(m,2h),3.25(d,j＝2.2hz,2h),2.83-2.75(m,2h), 2.52-2.39(m,2h),1.61(s,3h),1.38(t,j＝7.1hz,3h),1.09(s,9h)；
13
c nmr(151mhz,cdcl3)δ204.4(q,j ＝4.0hz),170.9,170.7,166.2,140.2,139.9,129.9,129.7,126.7,123.5(q,j＝274.7hz),115.9,108.0,100.1(q, j＝34.0hz),73.0,61.0,58.6,56.4,52.5,52.4,39.4,32.3,28.9,27.4,23.4,14.3；
19
f nmr(565mhz,cdcl3)δ
ꢀ‑
63.49；
[0287]
实施例66
[0288]
[0289]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴化物2a(55.0mg,0.24mmol)，碳氢键化合物3l(171.2mg,1mmol)和丙酮(0.5ml)。紫光灯(10 w,390nm)照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物69(54.0mg,42％yield,d.r.＝ 1.2/1)。
[0290]
major diastereoisomer(29.4mg):1h nmr(600mhz,cdcl3)δ8.02(d,j＝8.1hz,2h),7.39(d,j＝8.2 hz,2h),4.84(d,j＝8.6hz,1h),4.66(s,1h),4.38(q,j＝7.1hz,2h),3.93-3.83(m,1h),3.64(d,j＝7.4hz, 3h),3.46(d,j＝34.8hz,3h),3.32-3.21(m,4h),2.78(s,2h),1.85-1.71(m,4h),1.62(s,3h),1.52-1.48(m, 2h),1.44-1.41(m,9h),1.41-1.39(m,3h)；
13
c nmr(151mhz,cdcl3)δ204.8(q,j＝5.0hz),171.2,171.1, 170.9,170.7,170.3,166.1,166.1,154.2,140.3,139.9,139.5,130.2,129.8,126.9,126.8,123.5(q,j＝274.4hz), 115.6,109.1,108.8,99.2(q,j＝36.2hz),79.7,79.2,61.2,60.4,56.5,56.3,55.4,55.3,52.7,52.6,52.3,46.6,46.2, 39.6,39.4,33.0,32.8,31.4,30.3,30.1,29.5,28.5,23.5,23.5,22.7,21.1,14.3,14.2；
19
f nmr(565mhz,cdcl3) δ-63.53,-63.77(rotamer)；
[0291]
minor diastereoisomer(24.6mg):1h nmr(600mhz,cdcl3)δ8.00(d,j＝8.0hz,2h),7.42-7.35(m, 2h),4.84(s,1h),4.64(s,1h),4.37(q,j＝7.1hz,2h),3.88-3.76(m,1h),3.62(d,j＝7.4hz,3h),3.45(d,j＝ 34.8hz,3h),3.30-3.17(m,4h),2.77-2.70(m,2h),2.12-2.02(m,1h),1.71-1.66(m,2h),1.60(s,3h),1.51-1.44 (m,3h),1.43-1.40(m,9h),1.39-1.37(m,3h)；
13
c nmr(151mhz,cdcl3)δ205.5,205.5,170.9,170.6,166.1, 166.1,154.3,140.4,140.3,139.8,139.6,130.2,129.9,126.8,126.6,123.6(d,j＝274.7hz),115.8,115.6,108.1, 99.8,99.5,79.7,61.2,56.5,56.4,55.9,55.6,52.7,52.5,46.7,46.2,39.6,32.4,32.3,31.1,29.8,29.4,28.5,28.5, 28.4,23.4,23.4,22.6,14.3；
19
f nmr(565mhz,cdcl3)δ-63.11；
[0292]
hrms:(esi)calcd for c
33h43
f3no
8
[m h]

638.2935；found 638.2922.
[0293]
实施例67
[0294][0295]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴化物2a(55.0mg,0.24mmol)，碳氢键化合物3m(199.3mg,1mmol)和丙酮(0.5ml)。紫光灯(10 w,390nm)照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物70(58.5mg,44％yield,d.r.＝ 2.3/1)。
[0296]1h nmr(600mhz,cdcl3)δ8.05-7.96(m,2h),7.43-7.32(m,2h),4.86-4.82(m,1h),4.68-4.61(m,1h), 4.35(q,j＝7.1hz,2h),4.22-4.05(m,1h),3.60(d,j＝20.6hz,3h),3.44(d,j＝33.8hz,3h),3.30-3.18(m, 2h),2.94(s,1h),2.73(s,2h),2.54-2.17(m,7h),
1.59(s,3h),1.50-1.44(m,5h),1.41-1.36(m,7h)；
13
c nmr (151mhz,cdcl3)δ207.1,205.3(q,j＝2.8hz),170.8,170.6,166.1,166.0,154.3,140.2,140.2,139.3,130.3, 129.9,129.9,127.0,126.8,123.4(q,j＝274.7hz),116.0,115.7,109.2,97.8(q,j＝30.6hz),80.9,61.1,61.1, 56.5,52.6,52.6,52.4,52.4,44.7,39.8,32.9,28.3,28.2,23.4,23.4,14.3.
19
f nmr(565mhz,cdcl3)δ-62.53,
ꢀ‑
62.91,-63.26(rotamer)；hrms:(esi)calcd for c
34h43
f3no
9
[m h]

666.2884；found 666.2870.
[0297]
实施例68
[0298][0299]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴化物2a(55.0mg,0.24mmol)，碳氢键化合物3n(290.4mg,2mmol)和丙酮(0.5ml)。紫光灯(10 w,390nm)照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物71(70.9mg,58％yield)。
[0300]1h nmr(600mhz,cdcl3)δ8.00(d,j＝8.0hz,2h),7.37(d,j＝8.4hz,2h),4.83(s,1h),4.68-4.62(m, 1h),4.36(q,j＝7.1hz,2h),3.62(s,3h),3.51(s,3h),3.34-3.19(m,4h),2.87-2.75(m,5h),2.52-2.33(m,2h), 1.60(s,3h),1.40(s,9h),1.38(t,j＝7.1hz,3h)；
13
c nmr(151mhz,cdcl3)δ204.2(q,j＝4.2hz),170.9, 170.6,166.1,155.5,155.4,140.2,139.6,130.2,129.9,126.6,126.5,123.4(q,j＝274.5hz),116.03,115.96, 108.8,108.7,99.7(q,j＝31.7hz),79.8,79.6,61.1,56.4,52.6,52.5,47.6,46.8,39.7,34.8,34.4,32.7,32.6,29.7, 28.4,28.3,26.2,25.3,23.3,14.3；
19
f nmr(565mhz,cdcl3)δ-63.45,-63.49(rotamer)；hrms:(esi)calcd for c
31h41
f3no
8
[m h]

612.2779；found 612.2780.
[0301]
实施例69
[0302][0303]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1i(63.7mg,0.2mmol)，芳基溴化物2a(55.0mg,0.24mmol)，硅氢化合物3o(136.3mg,1mmol)和丙酮(0.5ml)。紫光灯(10w, 390nm)照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物72(60.2mg,50％yield)。
[0304]1h nmr(600mhz,cdcl3)δ7.95(d,j＝8.5hz,2h),7.37-7.34(m,2h),7.33-7.29(m,
烯炔化合物1i(63.7mg,0.2mmol)，芳基溴化物2a(55.0mg,0.24mmol)，碳氢化合物3q(240.0mg,2mmol)和丙酮(0.5ml)。紫光灯(10 w,390nm)照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物74(55.1mg,50％yield,d.r.＝ 1/1)。
[0313]
major diastereoisomer(28.9mg):1h nmr(600mhz,cdcl3)δ8.03(d,j＝8.4hz,2h),7.35(d,j＝8.5 hz,2h),4.86(s,1h),4.69-4.63(m,1h),4.38(q,j＝7.1hz,2h),3.63(s,3h),3.48(s,3h),3.30-3.17(m,2h), 3.14-3.08(m,1h),3.01-2.93(m,2h),2.80-2.73(m,2h),2.62-2.52(m,2h),2.48-2.42(m,1h),2.38-2.32(m, 1h),2.31-2.24(m,1h),1.84-1.76(m,1h),1.61(s,3h),1.40(t,j＝7.1hz,3h)；
13
c nmr(151mhz,cdcl3)δ 204.4(q,j＝4.0hz),170.9,170.6,166.0,140.2,139.2,130.8,130.2,126.7,124.2(q,j＝274.3hz),116.1,110.2, 99.6(q,j＝34.4hz),61.4,56.5,56.3,52.8,52.6,51.8,40.2,34.6,33.1,32.4,28.7,23.4,14.4；
19
f nmr(565 mhz,cdcl3)δ-63.56；
[0314]
minor diastereoisomer(26.2mg):1h nmr(600mhz,cdcl3)δ8.03(d,j＝8.4hz,2h),7.36(d,j＝8.5 hz,2h),4.86(s,1h),4.68-4.64(m,1h),4.38(q,j＝7.1hz,2h),3.64(s,3h),3.50(s,3h),3.30-3.18(m,2h), 3.16-3.08(m,2h),2.95-2.88(m,1h),2.77(d,j＝3.2hz,2h),2.63-2.58(m,1h),2.58-2.50(m,1h),2.47-2.33 (m,2h),2.21-2.14(m,1h),1.81-1.72(m,1h),1.61(s,3h),1.40(t,j＝7.1hz,3h)；
13
c nmr(151mhz,cdcl3) δ204.3(q,j＝3.8hz),170.9,170.7,166.0,140.2,139.2,130.8,130.2,126.7,123.4(q,j＝274.8hz),116.1, 110.2,99.6(q,j＝34.6hz),61.4,56.5,56.3,52.9,52.7,51.9,40.3,34.9,33.1,32.2,28.7,23.4,14.4；
19
f nmr (565mhz,cdcl3)δ-63.52；
[0315]
hrms:(esi)calcd for c
28h34
f3o8s

[m h]

587.1921；found 587.1925.
[0316]
实施例72
[0317][0318]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1k(88.0mg,0.3mmol)，酰氯2i’(30.9mg,0.2mmol)，碳氢化合物3r(154.0mg,1mmol)和丙酮(0.5ml)。紫光灯(10w,390nm) 照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物75(81.5mg,74％yield,d.r.＝1.1/1)。
[0319]
major diastereoisomer:1h nmr(600mhz,cdcl3)δ7.84(dd,j＝5.4,3.0hz,2h),7.72(dd,j＝5.4,3.0 hz,2h),7.58(d,j＝8.2hz,2h),7.19(d,j＝7.9hz,2h),3.97-3.86(m,2h),3.08-2.99(m,1h),2.79-2.71(m, 1h),2.38(s,3h),2.19-2.03(m,3h),1.65-1.61(m,1h),1.54-1.47(m,1h),1.42-1.34(m,2h),1.25-1.20(m,1h), 1.14(s,3h),1.02(s,3h),0.92-0.89(m,1h),0.88(s,3h),0.57(dd,j＝13.7,4.7hz,1h)；
[0320]
minor diastereoisomer:1h nmr(600mhz,chloroform-d)δ7.85(dd,j＝5.4,3.0hz,2h),7.72(dd,j＝ 5.5,3.0hz,2h),7.56(d,j＝8.1hz,2h),7.19(d,j＝7.9hz,2h),
4.00-3.88(m,2h),3.06
–
2.99(m,1h), 2.81-2.74(m,1h),2.37(s,3h),2.18(dd,j＝14.1,2.6hz,1h),1.91-1.82(m,1h),1.70(dd,j＝14.0,12.5hz, 1h),1.59(s,1h),1.50-1.40(m,2h),1.34-1.29(m,1h),1.26-1.22(m,2h),1.16(s,3h),1.01(s,3h),0.91(s, 3h),0.41(ddd,j＝13.7,6.1,2.3hz,1h)；
[0321]
hrms:(esi)calcd for c
33h35
f3no
4
[m h]

566.213；found 566.2502.
[0322]
实施例73
[0323][0324]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1k(88.0mg,0.3mmol)，酰氯2i’(30.9mg,0.2mmol)，碳氢化合物3s(250.0mg,1mmol)和丙酮(0.5ml)。紫光灯(10w,390nm) 照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物76(77.7mg,60％yield,d.r.＝1/1)。
[0325]1h nmr(600mhz,cdcl3)δ7.89-7.80(m,2h),7.75-7.68(m,2h),7.58(d,j＝8.0hz,2h),7.19(d,j＝ 7.9hz,2h),4.00-3.92(m,1h),3.92-3.86(m,1h),3.86-3.80(m,1h),3.07-2.99(m,1h),2.79-2.70(m,1h), 2.42-2.38(m,1h),2.37(s,3h),1.98-1.91(m,1h),1.86-1.79(m,1h),1.70-1.56(m,3h),1.41-1.34(m,2h), 1.33-1.21(m,3h),1.22-1.15(m,2h),1.14-1.06(m,2h),0.97(s,3h),0.88-0.85(m,1h),0.82(s,3h),0.78(s, 3h),0.69(s,3h)；
13
c nmr(151mhz,cdcl3)δ210.9(q,j＝3.9hz),192.0,168.3,143.5,135.0,134.0,132.1, 129.0,128.8,123.3,122.2(q,j＝274.8hz),110.4,99.6(q,j＝34.7hz),81.4,72.9,58.5,57.1,42.4,39.7,39.5, 36.0,35.9,33.54,33.52,33.0,28.3,27.5,21.7,21.4,21.1,20.5,18.3,14.8；
19
f nmr(565mhz,cdcl3)δ-64.05； hrms:(esi)calcd for c
39h45
f3no
4
[m h]

648.3295；found 648.3294.
[0326]
实施例74
[0327][0328]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1k(88.0mg,0.3mmol)，酰氯2i’(30.9mg,0.2mmol)，碳氢化合物3t(236.4mg,1mmol)和丙酮(0.5ml)。紫光灯(10w,390nm) 照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物77(64.7mg,50％yield,d.r.＝1.1/1)。
[0329]
major diastereoisomer:1h nmr(600mhz,cdcl3)δ7.89-7.80(m,2h),7.75-7.68(m,2h),7.58(d,j＝ 8.0hz,2h),7.19(d,j＝7.9hz,2h),4.00-3.92(m,1h),3.92-3.86(m,1h),3.86-3.80(m,1h),3.07-2.99(m,1h), 2.79-2.70(m,1h),2.42-2.38(m,1h),2.37(s,3h),1.98-1.91(m,1h),1.86-1.79(m,1h),1.70-1.56(m,3h), 1.41-1.34(m,2h),1.33-1.21(m,3h),1.22-1.15(m,2h),1.14-1.06(m,2h),0.97(s,3h),0.88-0.85(m,1h),0.82 (s,3h),0.78(s,3h),0.69(s,3h)；
13
c nmr(151mhz,cdcl3)δ210.9(q,j＝3.9hz),192.0,168.3,143.5, 135.0,134.0,132.1,129.0,128.8,123.3,122.2(q,j＝274.8hz),110.4,99.6(q,j＝34.7hz),81.4,72.9,58.5, 57.1,42.4,39.7,39.5,36.0,35.9,33.54,33.52,33.0,28.3,27.5,21.7,21.4,21.1,20.5,18.3,14.8；
19
f nmr(565 mhz,cdcl3)δ-64.05；
[0330]
minor diastereoisomer:1h nmr(600mhz,cdcl3)δ7.84(dd,j＝5.5,3.0hz,2h),7.71(dd,j＝5.4,3.0 hz,2h),7.63-7.59(m,2h),7.19(d,j＝7.9hz,2h),4.02-3.86(m,3h),3.05-2.96(m,1h),2.80-2.71(m,1h), 2.39(s,3h),2.30(dd,j＝14.9,5.5hz,1h),2.07(dd,j＝14.9,8.5hz,1h),1.86-1.81(m,1h),1.72-1.64(m, 1h),1.50-1.43(m,1h),1.44-1.37(m,2h),1.30-1.20(m,4h),1.19-1.12(m,1h),0.99(s,3h),0.92-0.86(m,2h), 0.85(s,3h),0.79(s,3h),0.73(s,3h)；
[0331]
13
c nmr(151mhz,cdcl3)δ211.3(q,j＝4.0hz),191.9,168.2,143.5,134.7,133.9,132.0,129.0,128.8,123.2, 122.7(q,j＝274.5hz),109.3,99.1(q,j＝34.5hz),81.4,72.9,58.5,57.1,42.3,39.68,39.67,36.0,35.9,34.4, 33.5,33.0,28.4,27.6,21.6,21.4,21.0,20.4,18.3,14.8；
19
f nmr(565mhz,cdcl3)δ-63.26；hrms:(esi) calcd for c
39h45
f3no
4
[m h]

648.3295；found 648.3294.
[0332]
实施例75
[0333][0334]
在惰性气氛下向装有磁子的反应管中加入十聚钨酸钠(13.3mg,0.004mmol)，(4,4'-二叔丁基-2,2'-联吡啶)二溴化镍(9.8mg,0.02mmol)，磷酸钾(84.8mg,0.4mmol)，1,3-烯炔化合物1k(88.0mg,0.3mmol)，酰氯2i’(30.9mg,0.2mmol)，碳氢化合物3u(136.1mg,1mmol)和丙酮(0.5ml)。紫光灯(10w,390nm) 照射在室温下反应12小时，浓缩，快速柱层析，得无色液体产物78(76.6mg,70％yield,r.r.＝1.3/1；d.r.＝1/1)。
[0335]1h nmr(600mhz,cdcl3)δ7.88-7.80(m,2h),7.75-7.68(m,2h),7.65-7.56(m,2h),7.25-7.14(m,2h), 4.67(d,j＝4.4hz,0.3h),4.56(s,0.2h),4.51-4.42(m,1h),3.99-3.85(m,2h),3.12-2.98(m,1h),2.84-2.72(m, 1h),2.57-2.47(m,0.5h),2.43-2.32(m,3h),2.08-1.81(m,3h),1.76-1.69(m,0.7h),1.67-1.60(m,0.3h), 1.58-1.35(m,2h),1.31-1.23(m,1h),1.15-1.08(m,1h),1.02-0.92(m,2h),0.92-0.82(m,4h),0.75-0.64(m, 0.5h),0.62-0.56(m,0.5h)；
13
c nmr(151mhz,cdcl3)δ210.9(q,j＝4.1hz),210.7(q,j＝4.2hz),210.6(q, j＝4.2hz),210.2(q,j＝3.8hz),192.1,192.04,191.95,168.2,164.51,
164.49,164.49,164.45,143.7,143.62, 143.59,143.57,134.96,134.95,134.87,134.78,134.0,132.0,129.10,129.08,129.06,128.96,128.89,128.87, 128.85,128.81,128.78,123.2,122.90(q,j＝274.7hz),122.88(q,j＝275.3hz),122.87(q,j＝274.7hz), 122.85(q,j＝274.7hz),109.9,109.5,109.4,109.2,101.5(q,j＝33.8hz),100.2,100.14,100.08,52.0,51.7, 51.2,50.8,48.24,48.17,46.8,46.7,41.92,41.91,41.2,41.1,38.8,37.0,36.8,36.1,36.02,35.99,35.97,34.1, 34.00,33.97,33.8,33.7,33.5,33.4,33.3,32.8,32.7,32.1,31.9,29.4,29.3,29.2,28.69,28.66,28.6,25.6,25.5, 24.9,24.8,21.7,21.7；
19
f nmr(565mhz,cdcl3)δ-62.97,-63.11,-63.23,-63.54；hrms:(esi)calcd for c
33h33
f3no
3
[m h]

548.2401；found 548.2394.
[0336]
以上列举的仅是本发明的几个具体实施例，显然，本发明不仅限于以上实施例，还可以有诸多变形，本领域的普通技术人员能从本发明公开的内容直接导出或间接联想到的所有变形，均应认为是本发明的保护范围。