本发明涉及新型单膦配体的制备方法。
背景技术：
过渡金属催化反应与配体的开发密切相关，膦配体作为日渐热门的交叉偶联领域应用最广泛的配体也越来越受到合成化学家的重视，由Buchwald课题组开发的联苯类二烷基(芳基)单膦配体在钯催化的碳—碳键和碳—杂键的构建反应中有着非常出色的应用(Aranyos,A.；Old,D.W.；Kiyomori,A.；Wolfe,J.P.；Sadighi,J.P.；Buchwald,S.L.J.Am.Chem.Soc.1999,121,4369)。但其在合成大位阻芳基取代联苯类单膦配体过程中存在步骤冗长(第一步合成联苯硼酸，第二步Suzuki反应，第三步交叉偶联反应制备膦配体)、结构单一、总产率低等问题。这些问题极大地影响了该类配体的开发与应用。
技术实现要素：
针对上述问题，本发明提供了一种新的芳基取代联苯型、吡咯型、吲哚型和联萘型单膦配体制备方法，该方法步骤简单(一步构建芳基取代单膦配体)，产率高，适用于快速构建新型单膦配体库。
本发明解决该技术问题所采取的技术方案是：
一种芳基取代联苯型、苯基吡咯型、苯基吲哚型或联萘型单膦配体制备方法，其特征在于，包括如下步骤：
以联苯型、吡咯型、吲哚型或联萘型单膦配体为原料，在惰性气体保护下，于有机溶液中，在无机碱的参与下，控制反应温度70～150℃,原料与芳香卤代物经一价铑催化碳氢活化反应制备芳基取代联苯型、吡咯型、吲哚型或联萘型单膦配体。
所述芳香卤代物为氯代芳香化合物或溴代芳香化合物；
所述的芳香卤代物的芳香基团骨架为苯环、萘环、蒽环、呋喃环、噻吩环、吡啶环、吲哚环、喹啉环、苯并呋喃环或苯并噻吩环。
所述反应一价铑催化剂为(1,5-环辛二烯)氯铑(I)二聚体、双环辛烯氯化铑(I)二聚体、双(1,5-环辛二烯)-三氟甲磺酸铑、二(1,5-环辛二烯)四氟硼酸铑(I)、二聚合羟基(1,5-环辛二烯)铑(I)、三苯基膦氯化铑、四羰基二氯化二铑、二羰基乙酰丙酮铑(I)或二(乙烯)氯铑二聚体中的一种；优选催化剂为(1,5-环辛二烯)氯铑(I)二聚体。
所述的有机溶剂为甲苯、三氟甲苯、对二甲苯、间二甲苯、邻二甲苯、四氢呋喃或1,4-二氧六环中的一种或多种的混合；优选的溶剂为1,4-二氧六环。
所述的无机碱为磷酸钾、碳酸铯、叔丁醇锂、叔丁醇钠或叔丁醇钾中的一种；优选无机碱为叔丁醇锂。
所述的无机碱与原料摩尔比为2～3:1；优选的摩尔比为3:1。
所述惰性气体为氩气或氮气。
所述的催化剂与原料与芳香卤代物的摩尔比为1～5％:1:1～10。
所述的反应温度70～150℃，反应时间为24～96h。
上述方法，当所述的催化剂与原料与芳基卤代物的摩尔比为1～5％:1:1～10，70℃≤反应温度<140℃，反应时间为24～96h时，产物为单芳基取代的联苯型、苯基吡咯型、苯基吲哚型或联萘型单膦配体。
上述方法，当所述的催化剂与原料与芳基卤代物的摩尔比为2.5～5％:1:2.4～5，140℃≤反应温度≤150℃，反应时间为24～48h时，产物为双芳基取代的联苯型、苯基吡咯型或苯基吲哚型单膦配体。
上述制备方法的部分化学反应方程式如下：
其中，R1为异丙基、环己基、叔丁基或苯基；R2为氢原子、甲基、甲氧基或氮，氮-二甲基；X为氯或溴；Ar为骨架为苯环、萘环、蒽环、呋喃环、噻吩环、吡啶环、吲哚环、喹啉环、苯并呋喃环或苯并噻吩环的芳香基团。
本发明提供了一种新的芳基取代联苯型、吡咯型、吲哚型和联萘型单膦配体的合成路线，该合成路线原材料价廉易得，单元操作简单，设备要求低，适合快速构建新型单膦配体库。
本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。
具体实施方式
以下是本发明的具体实施例，对本发明的技术方案作进一步的描述，但本发明并不限于此实施例。
(1)2-二环己基膦-2'-苯基联苯的合成
法一：25mL Schlenk管中，加入2-二环己基膦联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％),叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯31.4mg(0.2mmol)。70℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品73.5mg粘稠物，收率86％。
法二：25mL Schlenk管中，加入2-二环己基膦联苯(CyJohnPhos)70.1mg(0.2mmol)，双环辛烯氯化铑(I)二聚体3.6mg(原料摩尔数的2.5％),磷酸钾127.4mg(0.6mmol)，置换氩气三次，氩气保护下加入甲苯1mL，溴苯31.4mg(0.2mmol)。70℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品43.6mg粘稠物，收率51％。
法三：25mL Schlenk管中，加入2-二环己基膦联苯(CyJohnPhos)70.1mg(0.2mmol)，二(1,5-环辛二烯)三氟甲磺酸铑(I)4.7mg(原料摩尔数的5％),碳酸铯195.5mg(0.6mmol)，置换氩气三次，氩气保护下加入三氟甲苯1mL，溴苯31.4mg(0.2mmol)。70℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品47.1mg粘稠物，收率55％。
法四：25mL Schlenk管中，加入2-二环己基膦联苯(CyJohnPhos)70.1mg(0.2mmol)，二(1,5-环辛二烯)四氟硼酸铑(I)4.1mg(原料摩尔数的5％),叔丁醇钠57.7mg(0.6mmol)，置换氮气三次，氮气保护下加入对二甲苯1mL，溴苯31.4mg(0.2mmol)。70℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品29.9mg粘稠物，收率35％。
法五：25mL Schlenk管中，加入2-二环己基膦联苯(CyJohnPhos)70.1mg(0.2mmol)，二聚合羟基(1,5-环辛二烯)铑(I)2.3mg(原料摩尔数的2.5％),叔丁醇钾67.3mg(0.6mmol)，置换氩气三次，氩气保护下加入间二甲苯1mL，溴苯31.4mg(0.2mmol)。70℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品19.7mg粘稠物，收率23％。
法六：25mL Schlenk管中，加入2-二环己基膦联苯(CyJohnPhos)70.1mg(0.2mmol)，三苯基膦氯化铑(I)9.3mg(原料摩尔数的5％),叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入邻二甲苯1mL，溴苯31.4mg(0.2mmol)。70℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品36.7mg粘稠物，收率43％。
法七：25mL Schlenk管中，加入2-二环己基膦联苯(CyJohnPhos)70.1mg(0.2mmol)，四羰基二氯化二铑(I)1.9mg(原料摩尔数的2.5％),叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入四氢呋喃1mL，溴苯31.4mg(0.2mmol)。70℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品52.1mg粘稠物，收率61％。
法八：25mL Schlenk管中，加入2-二环己基膦联苯(CyJohnPhos)70.1mg(0.2mmol)，二羰基乙酰丙酮铑(I)2.6mg(原料摩尔数的5％),叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯31.4mg(0.2mmol)。70℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品72.7mg粘稠物，收率85％。
法九：25mL Schlenk管中，加入2-二环己基膦联苯(CyJohnPhos)70.1mg(0.2mmol)，二(乙烯)氯铑二聚体(I)1.9mg(原料摩尔数的2.5％),叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯31.4mg(0.2mmol)。70℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品73.4mg粘稠物，收率86％。
1H NMR(400MHz,CDCl3)δ7.46–7.38(m,2H),7.38–7.31(m,4H),7.31–7.20(m,2H),7.19–7.05(m,5H),1.74–1.57(m,7H),1.52–1.45(m,2H),1.38(d,J＝8.8Hz,1H),1.22–0.85(m,10H),0.74(d,J＝13.3Hz,1H),0.16–0.02(m,1H).13C NMR(101MHz,CDCl3)δ149.54(d,J＝30.6Hz),141.69,141.10(d,J＝5.9Hz),140.80(d,J＝1.6Hz),134.26(d,J＝20.0Hz),132.75(d,J＝2.9Hz),131.97,131.49(d,J＝5.8Hz),130.32,129.79,127.79,127.55,126.26,126.11,125.97,36.47(d,J＝15.7Hz),32.65(d,J＝12.6Hz),30.80(d,J＝14.6Hz),30.06(d,J＝19.4Hz),28.66(d,J＝4.8Hz),28.25(d,J＝12.8Hz),27.57(d,J＝12.4Hz),27.48(d,J＝6.5Hz),27.09,26.99,26.34.31P NMR(162MHz,CDCl3)δ-11.79.
(2)2-二环己膦基-2'-(N,N-二甲胺)-6'-苯基联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺)联苯(DavePhos)78.7mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体1.0mg(原料摩尔数的1％)，叔丁醇锂32mg(0.4mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯47.1mg(0.3mmol)。100℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品81.8mg白色固体，收率87％。1H NMR(400MHz,CDCl3)δ7.52–7.47(m,1H),7.39(t,J＝7.8Hz,1H),7.20–7.03(m,10H),2.49(s,6H),2.01(d,J＝12.2Hz,1H),1.87–1.59(m,10H),1.34–1.11(m,10H),0.96–0.83(m,1H).13C NMR(101MHz,CDCl3)δ152.45(d,J＝1.8Hz),146.07(d,J＝31.2Hz),142.48,142.27,136.95(d,J＝17.5Hz),135.38(d,J＝5.8Hz),133.81(d,J＝6.3Hz),132.24(d,J＝3.1Hz),130.12,127.98,127.06,126.96,125.78,125.76,124.63,117.40,44.43,35.32(d,J＝15.5Hz),34.14(d,J＝14.7Hz),32.19(d,J＝20.2Hz),30.68(d,J＝14.1Hz),30.01(d,J＝15.8Hz),28.39(d,J＝6.9Hz),28.18(d,J＝13.7Hz),27.76(d,J＝6.5Hz),27.45(d,J＝10.0Hz),27.16(d,J＝10.0Hz),26.58,26.39.31P NMR(162MHz,CDCl3)δ-8.89.
(3)2-二环己基膦基-2'-甲氧基-6'-苯基联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-甲氧基联苯76.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％),叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯47.1mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品59.0mg浅黄色固体，收率65％。1H NMR(400MHz,CDCl3)δ7.42(t,J＝8.0Hz,1H),7.37–7.30(m,3H),7.25(ddd,J＝8.9,4.2,2.2Hz,1H),7.17(dd,J＝8.1,1.4Hz,2H),7.13–7.03(m,4H),6.93(d,J＝7.8Hz,1H),3.71(s,3H),1.72–1.46(m,10H),1.38(d,J＝9.8Hz,1H),1.21–0.89(m,9H),0.71(d,J＝13.1Hz,1H),0.19–0.07(m,1H).13C NMR(101MHz,CDCl3)δ157.09(d,J＝0.6Hz),144.60(d,J＝30.8Hz),142.27(d,J＝2.4Hz),141.56(d,J＝1.1Hz),135.29(d,J＝18.5Hz),132.78(d,J＝6.0Hz),132.53(d,J＝3.2Hz),130.43,129.75(d,J＝6.1Hz),128.39,127.32,127.27,126.14,125.93,122.39,108.81,55.08,35.71(d,J＝15.2Hz),32.40(d,J＝12.8Hz),30.10(d,J＝19.0Hz),29.40(d,J＝7.3Hz),29.29(d,J＝10.6Hz),28.45(d,J＝13.1Hz),27.75(d,J＝9.4Hz),27.66(d,J＝6.9Hz),27.12(d,J＝2.1Hz),27.02(d,J＝3.8Hz),26.43,26.37.31P NMR(162MHz,CDCl3)δ-10.29.
(4)2-二苯基膦基-2'-苯基联苯的合成
25mL Schlenk管中，加入2-二苯基膦联苯(PhJohnPhos)67.7mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体1.0mg(原料摩尔数的1％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯31.4mg(0.2mmol)。90℃搅拌48小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品69.3mg白色固体，收率84％。1H NMR(400MHz,CDCl3)δ7.46–7.36(m,2H),7.30–7.22(m,4H),7.22–7.12(m,13H),7.01–6.93(m,2H),6.86–6.78(m,2H).13C NMR(101MHz,CDCl3)δ147.93(d,J＝32.3Hz),141.51(d,J＝1.0Hz),140.93(d,J＝1.6Hz),140.14(d,J＝6.8Hz),138.22(d,J＝13.4Hz),137.44(d,J＝12.9Hz),136.37(d,J＝12.4Hz),134.33(d,J＝2.0Hz),133.76(d,J＝20.1Hz),133.05(d,J＝19.0Hz),131.28(d,J＝3.3Hz),131.05(d,J＝5.9Hz),130.08(d,J＝1.4Hz),129.83,128.36,128.27,128.20,128.15,128.09,127.80(d,J＝5.2Hz),127.51,127.22,126.35,126.22.31P NMR(162MHz,CDCl3)δ-14.25.
(5)2-二苯基膦基-2'-(N,N-二甲胺基)-6'-苯基联苯的合成
25mL Schlenk管中，加入2-二苯基膦基-2'-(N,N-二甲胺基)联苯76.3mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂32mg(0.4mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯47.1mg(0.3mmol)。120℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品56.9mg白色固体，收率62％。1H NMR(400MHz,CDCl3)δ7.41(t,J＝7.8Hz,1H),7.33–7.27(m,6H),7.25–7.22(m,3H),7.16–7.01(m,9H),7.01–6.97(m,2H),6.95–6.90(m,1H),2.09(s,6H).13C NMR(101MHz,CDCl3)δ152.62,146.01(d,J＝35.1Hz),142.40(d,J＝43.0Hz),140.26(d,J＝15.1Hz),139.00(d,J＝12.2Hz),137.04(d,J＝9.6Hz),135.91(d,J＝2.8Hz),134.62(d,J＝5.9Hz),133.55(d,J＝20.1Hz),132.87,132.78,132.69,129.87,128.55,128.24,128.07(d,J＝6.2Hz),127.90(d,J＝2.9Hz),127.87(d,J＝2.3Hz),127.42,127.27,126.43,125.85,124.79,117.53,43.19.31P NMR(162MHz,CDCl3)δ-14.20.ATR-FTIR(cm-1):3454,2938,2823,2777,1634,1584,1432,1401,957,761,743,697,508,492.HRMS(ESI)m/z calcd for C32H29NP(M+H)+458.2032,found458.2034.
(6)2-二苯基膦基-2'-苯基-6'-甲基联苯的合成
25mL Schlenk管中，加入2-二苯基膦基-2'-甲基联苯70.5mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯47.1mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品69.9mg白色固体，收率83％。1H NMR(400MHz,CDCl3)δ7.39–7.31(m,3H),7.29–7.21(m,4H),7.21–7.06(m,12H),7.05–7.01(m,1H),6.64–6.55(m,2H),1.69(s,3H).13C NMR(101MHz,CDCl3)δ146.46(d,J＝33.4Hz),142.01(d,J＝1.5Hz),141.69(d,J＝2.3Hz),139.57(d,J＝6.5Hz),138.23(d,J＝13.5Hz),137.06(d,J＝5.9Hz),137.03(d,J＝1.5Hz),136.93(d,J＝3.7Hz),134.51(d,J＝2.4Hz),134.47,134.26,132.52(d,J＝17.9Hz),131.53(d,J＝6.2Hz),130.39(d,J＝1.5Hz),128.80,128.56,128.29,128.18(d,J＝7.3Hz),127.93(d,J＝5.4Hz),127.56,127.41(d,J＝4.1Hz),127.21,127.19,125.90,20.75.31P NMR(162MHz,CDCl3)δ-14.98.
(7)2-二叔丁基膦基-2'-苯基联苯的合成
25mL Schlenk管中，加入2-二叔丁基膦联苯(JohnPhos)59.7mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯62.8mg(0.4mmol)。138℃搅拌24小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品53.4mg无色粘稠物，收率71％。1H NMR(400MHz,CDCl3)δ7.58(d,J＝7.7Hz,1H),7.52–7.45(m,1H),7.44–7.38(m,2H),7.36(dd,J＝7.7,1.5Hz,1H),7.33–7.27(m,2H),7.24–7.06(m,6H),0.93(d,J＝11.2Hz,9H),0.70(d,J＝11.7Hz,9H).13C NMR(101MHz,CDCl3)δ149.96(d,J＝33.4Hz),142.42(d,J＝1.9Hz),140.95(d,J＝3.3Hz),135.63(d,J＝2.7Hz),132.83,132.01(d,J＝6.7Hz),131.12,130.56,129.97,127.96,127.81,127.32,127.24,126.14,125.88,125.66,33.36(d,J＝23.7Hz),31.00(d,J＝25.7Hz),30.84(d,J＝15.6Hz),29.91(d,J＝14.4Hz).31P NMR(162MHz,CDCl3)δ21.09.
(8)2-异丙基膦基-2'-苯基联苯的合成
25mL Schlenk管中，加入2-二异丙基膦联苯54.0mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯31.4mg(0.2mmol)。110℃搅拌24小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品58.2mg无色粘稠物，气相色谱纯度83％。
(9)2-二环己基膦基-2'-苯基-N-苯基吡咯的合成
25mL Schlenk管中，加入2-二环己基膦基-N-苯基吡咯(PCy)67.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯31.4mg(0.2mmol)。110℃搅拌24小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品71.2mg浅黄色粘稠物，收率86％。1H NMR(400MHz,CDCl3)δ7.50–7.44(m,2H),7.38(ddd,J＝7.7,6.5,2.5Hz,1H),7.29(d,J＝7.3Hz,1H),7.22–7.17(m,3H),7.15–7.11(m,2H),6.95(dt,J＝3.2,2.1Hz,1H),6.32(d,J＝2.1Hz,2H),1.68–1.37(m,12H),1.20–0.82(m,11H),0.35(s,1H).13C NMR(101MHz,CDCl3)δ139.82(d,J＝1.1Hz),139.02,138.56,130.67,129.98,128.66,128.58,128.46,128.08,127.18,126.95,126.69,116.22(d,J＝4.5Hz),108.86,35.23(d,J＝6.3Hz),33.16,30.87(d,J＝10.6Hz),29.60(d,J＝16.1Hz),29.46(d,J＝12.6Hz),28.90(d,J＝11.8Hz),28.12,27.52,27.38,27.19,26.90,26.38.31P NMR(162MHz,CDCl3)δ-26.54.
(10)2-二环己基膦基-2'-甲氧基-6'-苯基-N-苯基吡咯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-甲氧基-N-苯基吡咯(POMeCy)73.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯47.1mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品67.8mg浅黄色固体，收率76％。1H NMR(400MHz,CDCl3)δ7.42(t,J＝8.1Hz,1H),7.21–7.14(m,5H),7.08(dd,J＝7.8,1.1Hz,1H),7.01–6.90(m,2H),6.43–6.35(m,1H),6.28(dd,J＝3.5,1.5Hz,1H),3.75(s,3H),1.68–1.54(m,6H),1.49–1.36(m,4H),1.16–0.82(m,11H),0.32–0.17(m,1H).13C NMR(101MHz,CDCl3)δ156.18,141.73(d,J＝2.2Hz),139.11(d,J＝1.5Hz),129.12,128.88,128.43(d,J＝6.3Hz),127.94,127.49(d,J＝1.7Hz),127.37(d,J＝1.3Hz),126.95,122.41,115.56(d,J＝4.6Hz),109.88,108.61,55.40,34.74(d,J＝10.4Hz),33.04(d,J＝5.5Hz),29.67(d,J＝14.8Hz),29.49(d,J＝14.8Hz),28.86(d,J＝13.5Hz),28.41(d,J＝5.0Hz),27.65(d,J＝12.6Hz),27.37(d,J＝6.6Hz),27.17(d,J＝1.8Hz),27.06(d,J＝1.6Hz),26.47,26.40.31P NMR(162MHz,CDCl3)δ-25.77.
(11)2-二环己基膦基-2'-苯基-N-苯基吲哚的合成
25mL Schlenk管中，加入2-二环己基膦基-N-苯基吲哚(PInCy)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯31.4mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品74.4mg无色粘稠物，收率80％。1H NMR(400MHz,CDCl3)δ7.70–7.64(m,1H),7.57(dtd,J＝9.0,7.7,1.5Hz,2H),7.46(td,J＝7.5,1.8Hz,1H),7.34(dd,J＝7.7,1.0Hz,1H),7.23–7.15(m,3H),7.11–7.01(m,3H),6.95(dd,J＝8.0,1.4Hz,2H),6.67(s,1H),1.71–1.46(m,10H),1.39(d,J＝9.3Hz,1H),1.19–0.94(m,8H),0.89–0.75(m,2H),0.36–0.17(m,1H).13C NMR(101MHz,CDCl3)δ141.56(d,J＝2.6Hz),140.84(d,J＝2.8Hz),138.97(d,J＝1.9Hz),137.24(d,J＝13.4Hz),135.92(d,J＝1.7Hz),131.23,131.16(d,J＝0.6Hz),128.93,128.60,128.10,128.05,127.57,126.94,122.18,120.30,119.81,110.95(d,J＝1.4Hz),109.40(d,J＝4.9Hz),35.09(d,J＝12.2Hz),32.80(d,J＝6.6Hz),30.78(d,J＝14.8Hz),29.27(d,J＝15.0Hz),28.75(d,J＝14.4Hz),27.97(d,J＝2.2Hz),27.49(d,J＝13.0Hz),27.16(d,J＝5.4Hz),27.04(d,J＝2.7Hz),26.93(d,J＝3.4Hz),26.33,26.24.31P NMR(162MHz,CDCl3)δ-24.49.
(12)2-(2'-二环己基膦基)苯基-3-苯基-N-甲基吲哚的合成
25mL Schlenk管中，加入2-(2'-二环己基膦基)苯基-N-甲基吲哚(CM-Phos)80.7mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯47.1mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品90.3mg白色固体，收率94％。1H NMR(400MHz,CDCl3)δ7.77(d,J＝7.9Hz,1H),7.48–7.42(m,2H),7.40–7.32(m,2H),7.28(t,J＝7.6Hz,3H),7.19(t,J＝7.5Hz,1H),7.15–7.06(m,3H),7.00(t,J＝7.4Hz,1H),3.39(s,3H),1.78(td,J＝11.8,3.0Hz,1H),1.62–1.52(m,4H),1.37(d,J＝15.3Hz,4H),1.24–0.89(m,8H),0.80–0.58(m,4H),0.22–0.08(m,1H).13C NMR(101MHz,CDCl3)δ139.91(d,J＝32.6Hz),138.63(d,J＝20.2Hz),137.62(d,J＝5.7Hz),136.62,135.82,133.20(d,J＝5.7Hz),132.97(d,J＝3.2Hz),129.55,128.08,128.05,127.88,126.65,125.07,121.67,119.83,119.61,115.62(d,J＝2.9Hz),109.43,34.64(d,J＝14.9Hz),34.31(d,J＝14.3Hz),30.73(d,J＝2.9Hz),30.39(d,J＝17.7Hz),29.78(d,J＝11.2Hz),29.40,29.27(d,J＝1.5Hz),27.30(d,J＝10.2Hz),27.18(d,J＝10.3Hz),27.09(d,J＝1.8Hz),26.99(d,J＝4.9Hz),26.37,26.01.31P NMR(162MHz,CDCl3)δ-9.05.
(13)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(4-甲基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-甲基溴苯51.3mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品86.2mg无色粘稠物，收率89％。1H NMR(400MHz,CDCl3)δ7.53–7.46(m,1H),7.36(t,J＝7.8Hz,1H),7.18(td,J＝7.3,1.7Hz,1H),7.15–7.04(m,4H),7.00(d,J＝8.1Hz,2H),6.89(d,J＝7.9Hz,2H),2.47(s,6H),2.23(s,3H),1.98(d,J＝12.0Hz,1H),1.88–1.50(m,10H),1.34–1.07(m,10H),0.93–0.76(m,1H).13C NMR(101MHz,CDCl3)δ152.51(d,J＝1.8Hz),146.29(d,J＝31.2Hz),142.35,139.34,136.91(d,J＝17.7Hz),135.47(d,J＝5.6Hz),135.28,133.79(d,J＝6.3Hz),132.34(d,J＝3.1Hz),130.04,127.98,127.77,127.10,125.71,124.84,117.38,44.52,35.27(d,J＝15.5Hz),34.24(d,J＝14.9Hz),32.00(d,J＝19.4Hz),30.65(d,J＝14.2Hz),29.95(d,J＝15.5Hz),28.66(d,J＝8.1Hz),28.12(d,J＝13.2Hz),27.73(d,J＝6.9Hz),27.50(d,J＝10.1Hz),27.21(d,J＝9.9Hz),26.59,26.39,20.96.31P NMR(162MHz,CDCl3)δ-8.95.
(14)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(3-甲基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3-甲基溴苯51.3mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品78.2mg无色粘稠物，收率81％。1H NMR(400MHz,CDCl3)δ7.54–7.48(m,1H),7.39(t,J＝7.8Hz,1H),7.21–7.06(m,5H),7.02–6.88(m,4H),2.51(s,6H),2.19(s,3H),2.02(d,J＝11.8Hz,1H),1.86–1.56(m,10H),1.33–1.11(m,10H),0.97–0.84(m,1H).13C NMR(101MHz,CDCl3)δ152.41,146.12(d,J＝31.1Hz),142.60,142.14,136.86(d,J＝17.8Hz),136.34,135.19(d,J＝5.6Hz),133.77(d,J＝6.1Hz),132.25(d,J＝2.5Hz),130.78,127.91,127.34,126.98,126.78,126.53,125.69,124.64,117.23,44.43,35.35(d,J＝15.7Hz),34.12(d,J＝14.8Hz),32.13(d,J＝20.0Hz),30.67(d,J＝14.0Hz),30.11(d,J＝16.3Hz),28.47(d,J＝7.1Hz),28.16(d,J＝13.5Hz),27.75(d,J＝6.5Hz),27.35(d,J＝9.8Hz),27.18(d,J＝10.2Hz),26.58,26.42,21.12.31P NMR(162MHz,CDCl3)δ-8.77.
(15)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(3-异丙基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3-异丙基溴苯59.7mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品81.5mg无色粘稠物，收率80％。1H NMR(400MHz,CDCl3)δ7.49(dd,J＝6.6,1.6Hz,1H),7.39(t,J＝7.8Hz,1H),7.21–7.10(m,5H),7.07(t,J＝7.5Hz,1H),7.01(dt,J＝7.6,1.4Hz,1H),6.95(d,J＝7.5Hz,1H),6.89(s,1H),2.69(dt,J＝13.8,6.9Hz,1H),2.52(s,6H),1.96(d,J＝11.4Hz,1H),1.86–1.75(m,3H),1.74–1.51(m,7H),1.34–1.03(m,16H),0.86–0.72(m,1H).13C NMR(101MHz,CDCl3)δ152.57(d,J＝1.8Hz),147.27,146.22(d,J＝31.0Hz),142.65,142.03,136.77(d,J＝18.3Hz),135.35(d,J＝5.6Hz),133.78(d,J＝6.2Hz),132.45(d,J＝3.1Hz),128.55,127.98,127.91,127.19,127.00,125.71,124.86,123.73,117.58,44.63,35.26(d,J＝15.7Hz),34.21(d,J＝14.9Hz),33.86,31.72(d,J＝18.5Hz),30.45(d,J＝14.6Hz),29.86(d,J＝15.2Hz),28.92(d,J＝9.4Hz),28.06(d,J＝12.7Hz),27.66(d,J＝7.4Hz),27.33(d,J＝10.2Hz),27.19(d,J＝9.8Hz),26.58,26.34,23.86(d,J＝1.4Hz).31P NMR(162MHz,CDCl3)δ-8.98.
(16)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(4-甲氧基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-甲氧基溴苯56.1mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品95.7mg白色固体。1H NMR(400MHz,CDCl3)δ7.49–7.41(m,1H),7.35(t,J＝7.8Hz,1H),7.15(ddd,J＝17.1,11.2,4.2Hz,2H),7.10–6.99(m,5H),6.78–6.53(m,2H),3.71(s,3H),2.47(s,6H),1.96(d,J＝12.0Hz,1H),1.85–1.57(m,9H),1.30–1.06(m,11H),0.94–0.76(m,1H).13C NMR(101MHz,CDCl3)δ157.75,152.55(d,J＝1.7Hz),146.30(d,J＝31.2Hz),142.03(d,J＝0.8Hz),136.88(d,J＝17.6Hz),135.56(d,J＝5.6Hz),134.80,133.80(d,J＝6.2Hz),132.36(d,J＝3.1Hz),131.21,127.98,127.13(d,J＝0.9Hz),125.76,124.80,117.28,112.48,55.08,44.55,35.27(d,J＝15.4Hz),34.20(d,J＝14.8Hz),32.02(d,J＝19.5Hz),30.66(d,J＝14.3Hz),29.98(d,J＝15.6Hz),28.62(d,J＝8.0Hz),28.13(d,J＝13.3Hz),27.73(d,J＝6.9Hz),27.49(d,J＝10.0Hz),27.21(d,J＝9.9Hz),26.60,26.41.31P NMR(162MHz,CDCl3)δ-8.91.
(17)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(4-二甲氨基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-N,N-二甲基溴苯60.0mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品88.2mg浅黄色固体，收率86％。1H NMR(400MHz,CDCl3)δ7.51–7.46(m,1H),7.34(t,J＝7.8Hz,1H),7.21–7.10(m,3H),7.07(d,J＝7.8Hz,2H),6.98–6.92(m,2H),6.49–6.42(m,2H),2.85(s,6H),2.47(s,6H),1.94(d,J＝11.0Hz,1H),1.87–1.62(m,7H),1.58(d,J＝4.5Hz,1H),1.53(d,J＝3.5Hz,1H),1.31–1.07(m,11H),0.85–0.77(m,1H).13C NMR(101MHz,CDCl3)δ152.52,148.67,146.64(d,J＝31.1Hz),142.38,136.77(d,J＝17.7Hz),135.53(d,J＝5.7Hz),133.77(d,J＝6.1Hz),132.41(d,J＝2.4Hz),130.90,130.56,127.93,127.09,125.61,124.95,116.99,111.45,44.65,40.52,35.12(d,J＝15.5Hz),34.29(d,J＝15.0Hz),31.69(d,J＝18.5Hz),30.58(d,J＝14.3Hz),29.81(d,J＝15.0Hz),28.99(d,J＝9.7Hz),28.02(d,J＝12.6Hz),27.65(d,J＝7.7Hz),27.53(d,J＝10.4Hz),27.23(d,J＝9.8Hz),26.59,26.39.31P NMR(162MHz,CDCl3)δ-8.99.
(18)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(4-氟苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-氟溴苯52.5mg(0.2mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品84.6mg白色固体，收率87％。1H NMR(400MHz,CDCl3)δ7.51(d,J＝7.5Hz,1H),7.38(t,J＝7.8Hz,1H),7.22–7.00(m,7H),6.77(t,J＝8.7Hz,2H),2.50(s,6H),2.01(d,J＝12.1Hz,1H),1.90–1.58(m,10H),1.34–1.09(m,10H),0.93–0.83(m,1H).13C NMR(101MHz,CDCl3)δ161.26(d,J＝245.1Hz),152.56(d,J＝1.8Hz),145.93(d,J＝31.1Hz),141.42,138.24(d,J＝3.3Hz),136.92(d,J＝17.7Hz),135.44(d,J＝5.7Hz),133.73(d,J＝6.3Hz),132.33(d,J＝3.0Hz),131.58(d,J＝7.7Hz),128.04,127.17,125.90,124.52,117.55,113.79(d,J＝21.1Hz),44.44,35.35(d,J＝15.5Hz),34.04(d,J＝14.7Hz),32.23(d,J＝20.3Hz),30.65(d,J＝14.1Hz),30.08(d,J＝16.1Hz),28.28(d,J＝7.2Hz),28.18(d,J＝14.3Hz),27.76(d,J＝6.3Hz),27.40(d,J＝9.9Hz),27.13(d,J＝10.1Hz),26.55,26.39.31P NMR(162MHz,CDCl3)δ-8.92.19F NMR(377MHz,CDCl3)δ-117.25.
(19)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(3-氟苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3-氟溴苯52.5mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品66.6mg白色固体，收率68％。1H NMR(400MHz,CDCl3)δ7.53–7.48(m,1H),7.38(t,J＝7.8Hz,1H),7.18(td,J＝7.4,1.6Hz,1H),7.15–7.10(m,2H),7.08–6.99(m,3H),6.92–6.88(m,1H),6.86–6.81(m,1H),6.80–6.73(m,1H),2.49(s,6H),2.00(d,J＝12.4Hz,1H),1.85–1.59(m,10H),1.32–1.11(m,10H),0.97–0.86(m,1H).13C NMR(101MHz,CDCl3)δ161.86(d,J＝244.5Hz),152.56,145.69(d,J＝31.2Hz),144.55(d,J＝7.7Hz),141.26,136.93(d,J＝17.8Hz),135.28(d,J＝5.7Hz),133.65(d,J＝6.2Hz),132.38(d,J＝2.5Hz),128.26(d,J＝8.3Hz),128.09,127.21,126.00,125.90(d,J＝1.4Hz),124.29,117.80,117.03(d,J＝21.6Hz),112.67(d,J＝20.9Hz),44.40,35.39(d,J＝15.4Hz),34.08(d,J＝14.5Hz),32.25(d,J＝20.3Hz),30.74(d,J＝14.0Hz),30.10(d,J＝16.1Hz),28.28(d,J＝5.8Hz),28.19(d,J＝13.5Hz),27.77(d,J＝6.2Hz),27.30(d,J＝9.9Hz),27.14(d,J＝10.1Hz),26.55,26.37.31P NMR(162MHz,CDCl3)δ-8.91.19F NMR(377MHz,CDCl3)δ-115.12.
(20)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(2-氟苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，2-氟溴苯175mg(1.0mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品55.5mg无色粘稠物，收率57％。1H NMR(400MHz,CDCl3)δ7.45(dd,J＝5.5,3.6Hz,1H),7.36(t,J＝7.8Hz,1H),7.18–7.14(m,1H),7.13–6.96(m,6H),6.91(dd,J＝13.3,4.7Hz,1H),6.74(td,J＝7.5,1.0Hz,1H),2.48(s,6H),2.01(d,J＝12.9Hz,1H),1.89–1.60(m,10H),1.33–1.12(m,10H),1.03–0.94(m,1H).13C NMR(101MHz,CDCl3)δ159.56(d,J＝244.2Hz),152.50(d,J＝2.0Hz),145.92(d,J＝31.2Hz),136.76(d,J＝17.3Hz),136.26,135.85(d,J＝5.6Hz),132.55(dd,J＝6.4,2.5Hz),132.46(dd,J＝3.3,1.7Hz),131.95(d,J＝3.0Hz),129.88(d,J＝16.3Hz),128.17(d,J＝7.9Hz),127.72,127.32,125.93,124.35,122.45(d,J＝3.5Hz),117.55,114.73(d,J＝22.7Hz),44.14,35.63(d,J＝15.6Hz),34.25(d,J＝14.4Hz),32.60(d,J＝21.4Hz),31.00(d,J＝14.6Hz),30.18(d,J＝16.3Hz),28.36(d,J＝14.5Hz),27.93(d,J＝4.1Hz),27.88(d,J＝5.4Hz),27.47(d,J＝10.0Hz),27.17(d,J＝10.0Hz),26.59,26.48.31P NMR(162MHz,CDCl3)δ-9.39.19F NMR(377MHz,CDCl3)δ-113.34.
(21)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(4-三氟甲基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-三氟甲基溴苯67.5mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品92.3mg白色固体，收率86％。1H NMR(400MHz,CDCl3)δ7.48(d,J＝7.6Hz,1H),7.40(t,J＝7.8Hz,1H),7.32(d,J＝8.1Hz,2H),7.24–7.11(m,5H),7.09–7.00(m,2H),2.49(s,6H),1.96(d,J＝12.1Hz,1H),1.84–1.56(m,10H),1.31–1.06(m,10H),0.79–0.67(m,1H).13C NMR(101MHz,CDCl3)δ152.76,146.06,145.54(d,J＝31.1Hz),141.02,136.83(d,J＝18.0Hz),135.39(d,J＝5.7Hz),133.65(d,J＝6.1Hz),132.51(d,J＝2.4Hz),130.43,128.28,127.92(q,J＝32.2Hz),127.28,126.20,124.44,124.30(q,J＝273.7Hz),123.95(d,J＝3.5Hz),118.32,44.56,35.47(d,J＝15.5Hz),33.88(d,J＝14.6Hz),32.23(d,J＝20.0Hz),30.40(d,J＝13.8Hz),30.16(d,J＝16.6Hz),28.26(d,J＝5.8Hz),28.17(d,J＝13.6Hz),27.75(d,J＝6.3Hz),27.29(d,J＝9.8Hz),27.09(d,J＝10.3Hz),26.53,26.34.31P NMR(162MHz,CDCl3)δ-9.01.19F NMR(377MHz,CDCl3)δ-62.33.
(22)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(3-三氟甲基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3-三氟甲基溴苯67.5mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品95.4mg白色固体，收率89％。1H NMR(400MHz,CDCl3)δ7.48(d,J＝7.6Hz,1H),7.41(t,J＝7.8Hz,1H),7.37–7.27(m,3H),7.22–7.11(m,4H),7.11–7.02(m,2H),2.52(s,6H),1.96(d,J＝12.2Hz,1H),1.83–1.53(m,10H),1.32–1.06(m,10H),0.81–0.66(m,1H).13C NMR(101MHz,CDCl3)δ152.77(d,J＝2.0Hz),145.46(d,J＝30.8Hz),142.99,141.01,136.86(d,J＝18.6Hz),135.22(d,J＝5.7Hz),133.65,133.59,132.60(d,J＝3.1Hz),129.42(q,J＝32.0Hz),128.27,127.35,127.18,126.84(q,J＝3.6Hz),126.11,124.39,124.14(q,J＝272.6Hz),122.60(q,J＝3.8Hz),118.12,44.54,35.41(d,J＝15.7Hz),33.87(d,J＝14.6Hz),32.08(d,J＝19.7Hz),30.29(d,J＝7.4Hz),30.13(d,J＝4.0Hz),28.42(d,J＝7.0Hz),28.16(d,J＝13.4Hz),27.74(d,J＝6.6Hz),27.21(d,J＝8.4Hz),27.12(d,J＝10.3Hz),26.56,26.28.31P NMR(162MHz,CDCl3)δ-8.63.19F NMR(377MHz,CDCl3)δ-62.43.
(23)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(4-氰基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-氰基溴苯54.6mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝50:1洗脱，真空干燥后得产品74.4mg浅黄色固体，收率75％。1H NMR(400MHz,CDCl3)δ7.50(d,J＝7.7Hz,1H),7.45–7.33(m,3H),7.25–7.14(m,4H),7.12(t,J＝7.4Hz,1H),7.01(ddd,J＝7.6,3.4,1.1Hz,2H),2.50(s,6H),1.99(d,J＝12.3Hz,1H),1.87–1.79(m,4H),1.74–1.59(m,6H),1.35–1.08(m,10H),0.90–0.74(m,1H).13C NMR(101MHz,CDCl3)δ152.66,147.25,145.25(d,J＝31.0Hz),140.55,136.89(d,J＝18.1Hz),135.03(d,J＝5.6Hz),133.52(d,J＝6.1Hz),132.44(d,J＝2.2Hz),130.77,130.71,128.30,127.33,126.24,123.86,118.95,118.36,109.47,44.32,35.38(d,J＝15.4Hz),33.68(d,J＝14.5Hz),32.34(d,J＝20.8Hz),30.47(d,J＝13.6Hz),30.13(d,J＝16.8Hz),28.15(d,J＝14.2Hz),27.92(d,J＝4.8Hz),27.71(d,J＝5.8Hz),27.29(d,J＝9.6Hz),27.00(d,J＝10.4Hz),26.44,26.29.31P NMR(162MHz,CDCl3)δ-8.80.
(24)2-二环己基膦基-2'-(N,N-二甲胺)-6'-(3,5-二甲基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3,5-二甲基溴苯55.5mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品65.8mg白色固体，收率66％。1H NMR(400MHz,CDCl3)δ7.52(d,J＝7.5Hz,1H),7.38(t,J＝7.8Hz,1H),7.22–7.02(m,5H),6.74(s,3H),2.52(s,6H),2.17(s,6H),2.03(d,J＝12.2Hz,1H),1.86–1.70(m,8H),1.69–1.59(m,2H),1.38–1.10(m,10H),0.97–0.85(m,1H).13C NMR(101MHz,CDCl3)δ152.37(d,J＝1.9Hz),146.20(d,J＝31.0Hz),142.69,142.04,136.83(d,J＝18.2Hz),136.16,135.03(d,J＝5.6Hz),133.76(d,J＝6.2Hz),132.28(d,J＝3.1Hz),128.03,127.85,127.42,126.93,125.61,124.62,117.07,44.40,35.35(d,J＝15.8Hz),34.16(d,J＝14.9Hz),32.07(d,J＝19.9Hz),30.72(d,J＝13.7Hz),30.16(d,J＝16.6Hz),28.57(d,J＝7.6Hz),28.16(d,J＝13.4Hz),27.76(d,J＝6.7Hz),27.31(d,J＝8.2Hz),27.21(d,J＝8.9Hz),26.60,26.44,21.01.31P NMR(162MHz,CDCl3)δ-8.55.
(25)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(3,5-二三氟甲基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3,5-二三氟甲基溴苯87.9mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品100.8mg白色固体，收率83％。1H NMR(400MHz,CDCl3)δ7.58(s,1H),7.53(s,2H),7.48–7.40(m,2H),7.25–7.15(m,3H),7.12(ddd,J＝7.4,3.4,1.6Hz,1H),7.05(d,J＝7.5Hz,1H),2.55(s,6H),1.90(d,J＝12.2Hz,1H),1.81–1.58(m,9H),1.49(s,1H),1.27–0.98(m,10H),0.64–0.48(m,1H).13C NMR(101MHz,CDCl3)δ153.08(d,J＝2.0Hz),144.82(d,J＝30.3Hz),144.25,139.52,136.74(d,J＝19.5Hz),135.05(d,J＝5.6Hz),133.41(d,J＝5.9Hz),132.96(d,J＝3.0Hz),130.42,130.26(q,J＝33.3Hz),128.61,127.33,126.51,124.15,123.33(q,J＝272.8Hz),119.63(dq,J＝7.8,3.8Hz),118.96,44.64(s),35.44(d,J＝15.9Hz),33.45(d,J＝14.5Hz),31.98(d,J＝19.3Hz),30.39(d,J＝17.9Hz),29.73(d,J＝13.1Hz),28.37(d,J＝7.0Hz),28.13(d,J＝13.3Hz),27.71(d,J＝6.7Hz),27.07(d,J＝11.2Hz),26.95(d,J＝9.6Hz),26.52,26.15.31P NMR(162MHz,CDCl3)δ-8.22.19F NMR(377MHz,CDCl3)δ-62.76.
(26)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(3,5-二甲氧基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3,5-二甲氧基溴苯65.1mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品79.4mg白色固体，收率75％。1H NMR(400MHz,CDCl3)δ7.50–7.44(m,1H),7.37(t,J＝7.8Hz,1H),7.25–7.16(m,3H),7.12(ddd,J＝13.4,7.8,1.1Hz,2H),6.27(d,J＝2.3Hz,2H),6.20(t,J＝2.3Hz,1H),3.60(s,6H),2.50(s,6H),1.91(d,J＝10.9Hz,1H),1.77(t,J＝11.8Hz,3H),1.70–1.57(m,5H),1.49(t,J＝7.6Hz,2H),1.24–1.01(m,10H),0.82–0.69(m,1H).13C NMR(101MHz,CDCl3)δ159.52,152.71,146.10(d,J＝31.1Hz),144.06,142.20,136.77(d,J＝18.2Hz),135.53(d,J＝5.6Hz),133.58(d,J＝6.1Hz),132.58(d,J＝2.6Hz),128.06,126.89,125.90,124.75,118.18,108.79,98.62,55.19,44.81,35.29(d,J＝15.5Hz),34.29(d,J＝14.7Hz),31.49(d,J＝17.7Hz),30.55(d,J＝15.0Hz),29.80(d,J＝14.6Hz),29.15(d,J＝10.5Hz),27.97(d,J＝12.2Hz),27.58(d,J＝7.9Hz),27.30(d,J＝6.2Hz),27.20(d,J＝5.2Hz),26.55,26.39.31P NMR(162MHz,CDCl3)δ-9.07.
(27)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(2-萘基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，2-溴萘62.1mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品90.7mg白色固体，收率87％。1H NMR(400MHz,CDCl3)δ7.71–7.66(m,1H),7.64–7.60(m,1H),7.58(s,1H),7.49(d,J＝8.5Hz,1H),7.47–7.43(m,1H),7.42–7.32(m,3H),7.25–7.21(m,1H),7.15(s,1H),7.14–7.07(m,3H),7.03(t,J＝7.3Hz,1H),2.49(s,6H),1.98(d,J＝12.2Hz,1H),1.87–1.62(m,8H),1.55(s,1H),1.42(d,J＝3.6Hz,1H),1.30–1.11(m,8H),1.06–0.96(m,2H),0.87–0.77(m,1H).13C NMR(101MHz,CDCl3)δ152.57,146.04(d,J＝31.1Hz),142.34,139.96,136.87(d,J＝17.9Hz),135.47(d,J＝5.6Hz),133.74(d,J＝6.2Hz),132.87,132.41(d,J＝2.5Hz),131.66,128.77,128.74,128.08,127.76,127.31,127.21,126.07,125.85,125.54,125.33,124.97,117.56,44.49,35.45(d,J＝15.6Hz),34.10(d,J＝14.7Hz),32.17(d,J＝20.0Hz),30.64(d,J＝13.7Hz),30.17(d,J＝16.6Hz),28.45(d,J＝6.9Hz),28.18(d,J＝13.5Hz),27.77(d,J＝6.5Hz),27.30(d,J＝9.8Hz),27.13(d,J＝10.3Hz),26.58,26.36.31P NMR(162MHz,CDCl3)δ-8.64.
(28)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(4-(N-甲基)吲哚基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-溴-N-甲基吲哚63.0mg(0.3mmol)。138℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品80.8mg白色固体，收率77％。1H NMR(400MHz,CDCl3)δ7.50–7.45(m,1H),7.41–7.33(m,2H),7.16–7.03(m,5H),7.03–6.96(m,2H),6.94(d,J＝3.1Hz,1H),6.28(d,J＝3.0Hz,1H),3.69(s,3H),2.48(s,6H),2.02(d,J＝12.2Hz,1H),1.90–1.64(m,8H),1.59(d,J＝20.3Hz,2H),1.37–1.05(m,10H),1.00–0.92(m,1H).13C NMR(101MHz,CDCl3)δ152.35,146.61(d,J＝31.3Hz),143.61,136.91(d,J＝17.1Hz),135.63(d,J＝5.6Hz),135.18,133.84(d,J＝6.3Hz),133.58,132.19(d,J＝2.5Hz),128.58,127.75,127.67,127.13,125.49,125.44,124.37,122.44,116.73,107.44,100.78,44.44,35.35(d,J＝15.6Hz),34.28(d,J＝14.8Hz),32.73,32.24(d,J＝20.3Hz),30.83(d,J＝14.0Hz),30.08(d,J＝16.0Hz),28.46(d,J＝6.8Hz),28.21(d,J＝13.7Hz),27.80(d,J＝6.4Hz),27.49(d,J＝9.9Hz),27.20(d,J＝10.0Hz),26.61,26.44.31P NMR(162MHz,CDCl3)δ-8.92.
(29)2-二环己基膦基-2'-(N,N-二甲胺基)-6'-(9-蒽基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基-2'-(N,N-二甲胺基)联苯(DavePhos)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，9-溴蒽257.1mg(1.0mmol)。150℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品47.9mg白色固体，收率42％。1H NMR(400MHz,CDCl3)δ8.22(s,1H),7.96–7.74(m,4H),7.46(t,J＝7.8Hz,1H),7.42–7.35(m,2H),7.30(ddd,J＝9.1,6.8,3.1Hz,2H),7.26–7.22(m,1H),7.17–7.08(m,2H),7.02(dd,J＝7.5,1.1Hz,1H),6.77(td,J＝7.5,1.2Hz,1H),6.55(t,J＝7.5Hz,1H),2.51(s,6H),1.95(d,J＝12.1Hz,1H),1.83–1.63(m,8H),1.54(s,2H),1.32–0.98(m,9H),0.89–0.79(m,1H),0.31(d,J＝13.1Hz,1H).13C NMR(101MHz,CDCl3)δ153.23,144.99(d,J＝31.2Hz),139.21,137.15,136.56,132.55(d,J＝1.9Hz),132.14(d,J＝6.3Hz),131.14(d,J＝26.2Hz),130.50(d,J＝50.1Hz),129.38(d,J＝6.4Hz),128.12(d,J＝11.9Hz),127.66(d,J＝1.5Hz),126.24,125.94(d,J＝5.5Hz),125.36,125.21,124.70,124.55,124.40,117.28,44.26,36.34(d,J＝16.6Hz),33.40(d,J＝25.1Hz),33.20(d,J＝15.5Hz),30.62(d,J＝19.7Hz),28.72(d,J＝11.5Hz),28.59(d,J＝14.4Hz),28.05(d,J＝4.2Hz),27.76,27.21(d,J＝9.0Hz),27.11(d,J＝10.9Hz),26.63,26.27.31P NMR(162MHz,CDCl3)δ-10.30.
(30)2-二环己基膦基-2',6'-二苯基联苯的合成
法一：25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯75.4mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品94.5mg白色固体，收率94％。
法二：25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，氯苯112.6mg(1.0mmol)。150℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品92.6mg白色固体，收率92％。1H NMR(400MHz,CDCl3)δ7.49(dd,J＝8.4,6.9Hz,1H),7.40(s,1H),7.39–7.33(m,2H),7.25–7.18(m,5H),7.18–7.06(m,8H),1.70–1.58(m,4H),1.55–1.40(m,4H),1.16–0.91(m,12H),0.74–0.59(m,2H).13C NMR(101MHz,CDCl3)δ145.89(d,J＝30.9Hz),142.10,141.61(d,J＝1.7Hz),139.18(d,J＝5.6Hz),136.02(d,J＝18.3Hz),134.71(d,J＝6.1Hz),132.37(d,J＝2.8Hz),130.43,129.64,127.56,127.36,126.34(d,J＝0.8Hz),126.27,126.02,33.82(d,J＝15.0Hz),30.95(d,J＝17.3Hz),28.83(d,J＝10.8Hz),27.37(d,J＝12.2Hz),27.08,26.32.31P NMR(162MHz,CDCl3)δ-10.19.
(31)2-二苯基膦基-2',6'-二苯基联苯的合成
25mL Schlenk管中，加入2-二环己基膦基联苯(PhJohnPhos)67.7mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯75.4mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品84.6mg白色固体，收率86％。1H NMR(400MHz,CDCl3)δ7.52(dd,J＝8.2,7.1Hz,1H),7.43–7.36(m,2H),7.24–7.19(m,2H),7.17–7.03(m,9H),7.02–6.96(m,5H),6.93–6.88(m,4H),6.78–6.66(m,4H).13C NMR(101MHz,CDCl3)δ146.25(d,J＝33.6Hz),142.39(d,J＝1.9Hz),141.90(d,J＝0.9Hz),138.35(d,J＝6.2Hz),137.92,137.78,136.83(d,J＝12.8Hz),135.10(d,J＝2.7Hz),133.46(d,J＝19.5Hz),133.21(d,J＝6.7Hz),130.27,129.50,128.01,127.95,127.89,127.87,127.60,127.35,126.94,125.93.31P NMR(162MHz,CDCl3)δ-14.62.
(32)2-二环己基膦基-2',6'-二苯基-N-苯基吡咯的合成
25mL Schlenk管中，加入2-二环己基膦基-N-苯基吡咯(PCy)67.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯75.4mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品90.6mg白色固体，收率92％。1H NMR(400MHz,CDCl3)δ7.53(dd,J＝8.8,6.3Hz,1H),7.49–7.44(m,2H),7.22(s,10H),6.84(dd,J＝4.1,3.3Hz,1H),6.21–6.12(m,2H),1.68(s,2H),1.61–1.47(m,6H),1.27(d,J＝11.8Hz,2H),1.06–0.90(m,10H),0.84–0.70(m,2H).13C NMR(101MHz,CDCl3)δ140.91(d,J＝1.5Hz),139.34,136.22(d,J＝1.3Hz),130.28,129.60(d,J＝6.1Hz),128.86,128.50,127.89,127.05,115.90(d,J＝4.2Hz),108.47,34.24(d,J＝8.8Hz),30.83(d,J＝16.3Hz),28.80(d,J＝9.5Hz),27.32(d,J＝12.5Hz),27.02(d,J＝8.5Hz),26.32.31P NMR(162MHz,CDCl3)δ-25.42.
(33)2-二环己基膦基-2',6'-二苯基-N-苯基吲哚的合成
25mL Schlenk管中，加入2-二环己基膦基-N-苯基吲哚(PCy)77.9mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，溴苯75.4mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品95.1mg白色固体，收率88％。1H NMR(400MHz,CDCl3)δ7.62(dd,J＝8.5,6.7Hz,1H),7.53(dd,J＝9.9,8.7Hz,3H),7.16–6.91(m,13H),6.51(s,1H),1.72(s,2H),1.58(d,J＝14.0Hz,3H),1.46(d,J＝17.6Hz,3H).1.25(d,J＝13.2Hz,2H),1.09–0.73(m,12H).13C NMR(101MHz,CDCl3)δ142.40,141.81(d,J＝2.0Hz),139.25,138.10(d,J＝10.7Hz),133.58,130.77,129.06,128.64,127.82,127.55,127.00,122.13,120.24,119.49,111.86,109.18(d,J＝4.1Hz),34.00(d,J＝9.9Hz),30.89(d,J＝17.2Hz),28.52(d,J＝8.7Hz),27.24(d,J＝13.0Hz),26.94(d,J＝8.1Hz),26.26.31P NMR(162MHz,CDCl3)δ-23.51.
(34)2-二环己基膦基-2',6'-二(4-甲基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-甲基溴苯82.1mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品98.8mg白色固体，收率93％。1H NMR(400MHz,CDCl3)δ7.47(dd,J＝8.4,6.8Hz,1H),7.40–7.36(m,2H),7.36–7.32(m,1H),7.27–7.23(m,1H),7.20–7.12(m,2H),7.10–7.05(m,4H),6.93(d,J＝7.9Hz,4H),2.25(s,6H),1.74–1.58(m,4H),1.51–1.40(m,3H),1.18–0.88(m,13H),0.70–0.56(m,2H).13C NMR(101MHz,CDCl3)δ146.29(d,J＝31.1Hz),141.44,139.23,139.13,135.88(d,J＝18.2Hz),135.50,134.71(d,J＝6.1Hz),132.48(d,J＝2.1Hz),130.30,129.41,128.09,127.52,126.41,126.13,33.91(d,J＝14.9Hz),30.82(d,J＝16.9Hz),28.95(d,J＝11.2Hz),27.39(d,J＝12.0Hz),27.14(d,J＝8.3Hz),26.30,20.93.31P NMR(162MHz,CDCl3)δ-10.30.
(35)2-二环己基膦基-2',6'-二(3-甲基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3-甲基溴苯82.1mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品83.5mg白色固体，收率79％。1H NMR(400MHz,CDCl3)δ7.46(dd,J＝8.5,6.7Hz,1H),7.40–7.33(m,3H),7.20(dd,J＝5.4,3.7Hz,1H),7.18–7.09(m,2H),7.04(s,2H),7.01–6.94(m,4H),6.93–6.87(m,2H),2.21(s,6H),1.69–1.57(m,4H),1.56(s,2H),1.45(d,J＝10.7Hz,2H),1.19(td,J＝12.1,2.9Hz,2H),1.13–0.94(m,10H),0.66–0.54(m,2H).13C NMR(101MHz,CDCl3)δ146.22,145.91,142.03,141.69(d,J＝1.7Hz),138.98(d,J＝5.5Hz),136.70,135.86(d,J＝18.7Hz),134.73(d,J＝6.0Hz),132.47(d,J＝2.8Hz),131.40,129.51,127.66,127.46,127.11,126.75,126.15,33.90(d,J＝15.2Hz),30.71(d,J＝16.6Hz),29.09(d,J＝11.8Hz),27.41(d,J＝11.7Hz),27.18(d,J＝8.4Hz),26.39,21.31.31P NMR(162MHz,CDCl3)δ-9.80.
(36)2-二环己基膦基-2',6'-二(3-异丙基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3-异丙基溴苯95.5mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品104.6mg白色固体，收率89％。1H NMR(400MHz,CDCl3)δ7.54–7.39(m,4H),7.25–7.17(m,2H),7.17–7.08(m,5H),7.03–6.92(m,4H),2.69(dt,J＝13.7,6.7Hz,2H),1.58(d,J＝34.6Hz,6H),1.45(s,2H),1.17–0.96(m,24H),0.51(d,J＝7.8Hz,2H).13C NMR(101MHz,CDCl3)δ147.38,146.23(d,J＝30.8Hz),141.93,141.72,139.00(d,J＝5.5Hz),135.82(d,J＝18.9Hz),134.90(d,J＝6.2Hz),132.64,129.52,128.76,128.20,127.60,127.53,126.32,126.13,124.12,33.91,33.91(d,J＝15.2Hz),30.38(d,J＝16.5Hz),29.04(d,J＝11.9Hz),27.33(d,J＝11.8Hz),27.13(d,J＝8.6Hz),26.25,23.92,23.77.31P NMR(162MHz,CDCl3)δ-10.40.
(37)2-二环己基膦基-2',6'-二(4-甲氧基基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-甲氧基溴苯89.8mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品99.2mg白色固体，收率88％。1H NMR(400MHz,CDCl3)δ7.44(dd,J＝8.3,6.9Hz,1H),7.37–7.31(m,3H),7.27–7.22(m,1H),7.20–7.12(m,2H),7.12–7.08(m,4H),6.69–6.62(m,4H),3.72(s,6H),1.65(dd,J＝24.8,6.3Hz,4H),1.57(s,2H),1.47(s,2H),1.22–0.93(m,12H),0.70–0.55(m,2H).13C NMR(101MHz,CDCl3)δ157.96,146.32(d,J＝30.9Hz),141.15(d,J＝1.7Hz),139.19(d,J＝5.5Hz),135.89(d,J＝18.1Hz),134.69,134.62,132.53(d,J＝2.9Hz),131.47,129.21,127.51,126.49,126.20,112.83,55.10,33.88(d,J＝15.0Hz),30.88(d,J＝17.0Hz),28.95(d,J＝11.2Hz),27.42(d,J＝12.0Hz),27.15(d,J＝8.3Hz),26.34.31P NMR(162MHz,CDCl3)δ-9.98.
(38)2-二环己基膦基-2',6'-二(4-二甲氨基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-二甲氨基溴苯96.0mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品107.1mg白色固体，收率91％。1H NMR(400MHz,CDCl3)δ7.40(dd,J＝8.5,6.7Hz,1H),7.38–7.29(m,3H),7.27–7.22(m,1H),7.22–7.07(m,2H),7.08–6.97(m,4H),6.55–6.40(m,4H),2.84(s,12H),1.71–1.51(m,6H),1.43(s,2H),1.20–0.90(m,12H),0.70–0.53(m,2H).13C NMR(101MHz,CDCl3)δ148.76,147.06(d,J＝30.9Hz),141.47(d,J＝1.7Hz),138.94(d,J＝5.5Hz),135.80(d,J＝18.1Hz),134.72(d,J＝6.2Hz),132.55(d,J＝2.8Hz),131.12,130.68,128.64,127.41,126.43,125.88,111.71,40.52,33.90(d,J＝15.1Hz),30.69(d,J＝16.5Hz),29.09(d,J＝11.9Hz),27.44(d,J＝11.7Hz),27.16(d,J＝8.6Hz),26.34.31P NMR(162MHz,CDCl3)δ-9.96.
(39)2-二环己基膦基-2',6'-二(4-氟苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-氟溴苯84.0mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品89.9mg白色固体，收率92％。1H NMR(400MHz,CDCl3)δ7.46(dd,J＝8.2,7.1Hz,1H),7.35(d,J＝7.5Hz,2H),7.30(ddd,J＝6.9,3.7,1.7Hz,1H),7.27–7.22(m,1H),7.19–7.11(m,6H),6.87–6.72(m,4H),1.71–1.56(m,6H),1.50(d,J＝4.7Hz,2H),1.18–0.93(m,12H),0.73–0.57(m,2H).13C NMR(101MHz,CDCl3)δ161.51(d,J＝245.9Hz),145.54(d,J＝30.8Hz),140.64(d,J＝1.7Hz),139.20(d,J＝5.6Hz),137.95(d,J＝3.3Hz),135.97(d,J＝18.7Hz),134.47(d,J＝6.1Hz),132.60(d,J＝2.7Hz),131.92(d,J＝7.8Hz),129.66,127.68,126.62,126.57,114.24(d,J＝21.1Hz),33.85(d,J＝15.0Hz),30.98(d,J＝17.2Hz),28.83(d,J＝10.8Hz),27.37(d,J＝12.2Hz),27.12(d,J＝8.1Hz),26.29.31P NMR(162MHz,CDCl3)δ-10.01.19F NMR(376MHz,CDCl3)δ-116.88.
(40)2-二环己基膦基-2',6'-二(3-氟苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3-氟溴苯84.0mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品94.5mg白色固体，收率88％。1H NMR(400MHz,CDCl3)δ7.50(dd,J＝8.3,7.0Hz,1H),7.39(d,J＝7.4Hz,2H),7.33(ddd,J＝7.1,3.6,1.5Hz,1H),7.29–7.23(m,1H),7.23–7.13(m,2H),7.08(td,J＝7.9,6.2Hz,2H),7.00–6.88(m,4H),6.81(ddd,J＝8.3,2.5,1.2Hz,2H),1.73–1.57(m,6H),1.50(d,J＝6.1Hz,2H),1.24–0.88(m,12H),0.76–0.60(m,2H).13C NMR(101MHz,CDCl3)δ162.02(d,J＝244.7Hz),145.04(d,J＝30.8Hz),144.07(d,J＝7.7Hz),140.49,139.11(d,J＝4.7Hz),135.97(d,J＝18.7Hz),134.34(d,J＝5.9Hz),132.63(d,J＝1.5Hz),129.87,128.69(d,J＝8.3Hz),127.76,126.75,126.65,126.18(d,J＝1.5Hz),117.39(d,J＝21.9Hz),113.04(d,J＝20.9Hz),33.89(d,J＝14.7Hz),30.97(d,J＝17.1Hz),28.81(d,J＝10.7Hz),27.27(d,J＝12.2Hz),27.11(d,J＝8.2Hz),26.26.31P NMR(162MHz,CDCl3)δ-10.05.19F NMR(376MHz,CDCl3)δ-114.31.
(41)2-二环己基膦基-2',6'-二(2-氟苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，2-氟溴苯175.0mg(0.48mmol)。150℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品91.7mg白色固体，收率85％。1H NMR(400MHz,CDCl3)δ7.52–7.44(m,2H),7.40(dd,J＝6.9,1.3Hz,2H),7.18(d,J＝7.5Hz,1H),7.15–7.03(m,6H),6.99–6.90(m,2H),6.83(td,J＝7.6,1.0Hz,2H),1.71(d,J＝11.9Hz,2H),1.68–1.57(m,4H),1.53(d,J＝7.2Hz,2H),1.29–0.94(m,12H),0.85–0.71(m,2H).13C NMR(101MHz,CDCl3)δ159.66(d,J＝246.3Hz),145.28(d,J＝31.0Hz),140.86(d,J＝5.3Hz),135.90(d,J＝19.0Hz),135.76(d,J＝0.7Hz),133.32(dd,J＝5.6,2.9Hz),132.78(d,J＝2.2Hz),131.83(d,J＝2.5Hz),130.71(d,J＝2.0Hz),129.46(d,J＝14.9Hz),128.37(d,J＝8.1Hz),126.79,126.48,126.37,122.89(d,J＝3.6Hz),115.48(d,J＝22.8Hz),34.24(d,J＝15.4Hz),31.27(d,J＝17.9Hz),28.71(d,J＝10.2Hz),27.51(d,J＝12.5Hz),27.22(d,J＝7.7Hz),26.38.31P NMR(162MHz,CDCl3)δ-11.56.19F NMR(376MHz,CDCl3)δ-112.25.
(42)2-二环己基膦基-2',6'-二(4-三氟甲基苯基)联苯的合成
法一：25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-三氟甲基溴苯108.0mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品111.3mg白色固体，收率87％。
法二：25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-三氟甲基溴苯180.6mg(1.0mmol)。150℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品120.1mg白色固体，收率94％。1H NMR(400MHz,CDCl3)δ7.54(dd,J＝8.2,7.1Hz,1H),7.45–7.36(m,6H),7.32(dd,J＝11.6,5.9Hz,5H),7.25–7.16(m,3H),1.58(d,J＝25.8Hz,6H),1.49–1.39(m,2H),1.20–1.09(m,2H),1.08–0.86(m,10H),0.57–0.40(m,2H).13C NMR(101MHz,CDCl3)δ145.48,144.70(d,J＝30.5Hz),140.44,139.10(d,J＝5.2Hz),139.10(d,J＝5.2Hz),135.84(d,J＝19.5Hz),134.37(d,J＝5.9Hz),132.96(d,J＝1.9Hz),130.73,130.25,128.38(q,J＝32.2Hz),128.02,126.94(d,J＝24.2Hz),124.35(d,J＝3.4Hz),124.10(q,J＝251.9Hz),33.91(d,J＝14.9Hz),30.59(d,J＝16.1Hz),28.98(d,J＝11.7Hz),27.19(d,J＝11.8Hz),27.05(d,J＝8.8Hz),26.17.31P NMR(162MHz,CDCl3)δ-9.79.19F NMR(376MHz,CDCl3)δ-62.45.
(43)2-二环己基膦基-2',6'-二(3-三氟甲基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3-三氟甲基溴苯108.0mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品108.4mg白色固体，收率85％。1H NMR(400MHz,CDCl3)δ7.54(dd,J＝8.4,7.0Hz,1H),7.48–7.42(m,4H),7.38(t,J＝8.0Hz,4H),7.32(ddd,J＝6.2,3.3,1.6Hz,1H),7.26(d,J＝7.1Hz,2H),7.24–7.16(m,3H),1.59(d,J＝6.6Hz,4H),1.52(s,2H),1.44–1.39(m,2H),1.29–1.19(m,2H),1.05–0.88(m,10H),0.48–0.32(m,2H).13C NMR(101MHz,CDCl3)δ144.57(d,J＝30.0Hz),142.46,140.43,138.89(d,J＝5.3Hz),135.56(d,J＝20.2Hz),134.16(d,J＝5.7Hz),133.86,133.06(d,J＝1.9Hz),130.14,129.76(q,J＝31.3Hz),128.11,127.85,127.40(d,J＝3.2Hz),127.02(s),126.85,124.15(q,J＝289.3Hz),122.97(d,J＝3.4Hz),33.75(d,J＝15.1Hz),30.12(d,J＝15.6Hz),29.12(d,J＝12.5Hz),27.26(d,J＝11.3Hz),27.11(d,J＝9.1Hz),26.08.31P NMR(162MHz,CDCl3)δ-9.22.19F NMR(376MHz,CDCl3)δ-62.55.
(44)2-二环己基膦基-2',6'-二(4-氰基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-氰基溴苯87.4mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝20:1洗脱，真空干燥后得产品105.3mg白色固体，收率95％。1H NMR(400MHz,CDCl3)δ7.56(dd,J＝8.2,7.3Hz,1H),7.47–7.35(m,6H),7.31–7.27(m,4H),7.24(ddd,J＝6.0,5.1,2.8Hz,2H),7.21–7.15(m,2H),1.70–1.55(m,6H),1.51(d,J＝9.2Hz,2H),1.24–1.12(m,2H),1.09–0.91(m,10H),0.62–0.48(m,2H).13C NMR(101MHz,CDCl3)δ146.45,144.23(d,J＝30.3Hz),140.17(d,J＝1.8Hz),138.94(d,J＝5.4Hz),135.97(d,J＝20.3Hz),134.10(d,J＝5.9Hz),133.00(d,J＝2.7Hz),131.25,131.08,130.36,128.25,127.34,127.06,118.73,110.12,33.78(d,J＝15.1Hz),30.78(d,J＝16.6Hz),28.84(d,J＝11.0Hz),27.37(d,J＝11.9Hz),27.12(d,J＝8.3Hz),26.20.31P NMR(162MHz,CDCl3)δ-9.36.
(45)2-二环己基膦基-2',6'-二(3,5-二甲基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3,5-二甲基溴苯88.8mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品100.1mg白色固体，收率90％。1H NMR(400MHz,CDCl3)δ7.43(dd,J＝8.6,6.5Hz,1H),7.38–7.32(m,3H),7.26–7.18(m,1H),7.18–7.06(m,2H),6.81(s,4H),6.72(s,2H),2.14(s,12H),1.69–1.52(m,6H),1.44(d,J＝9.6Hz,2H),1.26–1.19(m,2H),1.10–0.93(m,10H),0.65–0.41(m,2H).13C NMR(101MHz,CDCl3)δ146.39,146.09,141.93,141.70(d,J＝1.7Hz),138.81(d,J＝5.7Hz),136.42,135.66(d,J＝19.0Hz),134.73(d,J＝6.0Hz),132.53(d,J＝2.8Hz),129.36,128.58,127.62,127.35,125.98,33.92(d,J＝15.3Hz),30.51(d,J＝16.1Hz),29.25(d,J＝12.4Hz),27.41(d,J＝11.4Hz),27.21(d,J＝8.8Hz),26.42,21.17.31P NMR(162MHz,CDCl3)δ-9.60.
(46)2-二环己基膦基-2',6'-二(3,5-二三氟甲基苯基)联苯的合成
法一：25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3,5-二三氟甲基溴苯140.6mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品137.7mg白色固体，收率89％。
法二：25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3,5-二三氟甲基氯苯248.6mg(1.0mmol)。150℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品142.4mg白色固体，收率94％。1H NMR(400MHz,CDCl3)δ7.63(t,J＝7.6Hz,7H),7.57–7.50(m,2H),7.26(t,J＝2.4Hz,2H),7.23–7.16(m,2H),1.64–1.50(m,6H),1.44–1.35(m,4H),1.05–0.85(m,10H),0.34–0.16(m,2H).13C NMR(101MHz,CDCl3)δ143.42(d,J＝28.5Hz),143.38,139.33,138.60(d,J＝4.8Hz),134.99(d,J＝22.8Hz),133.83(d,J＝1.5Hz),133.41(d,J＝5.4Hz),130.74,130.73(q,J＝33.2Hz),130.67,128.77,127.79,127.60,123.24(q,J＝272.8Hz),120.16(q,J＝2.2Hz),33.46(d,J＝15.4Hz),29.55(d,J＝13.8Hz),29.35(d,J＝13.8Hz),27.17(d,J＝4.2Hz),27.07(d,J＝3.6Hz),25.90.31P NMR(162MHz,CDCl3)δ-7.73.19F NMR(376MHz,CDCl3)δ-62.83.
(47)2-二环己基膦基-2',6'-二(3,5-二甲氧基苯基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3,5-二甲氧基溴苯104.2mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品90.9mg白色固体，收率73％。1H NMR(400MHz,CDCl3)δ7.52(ddd,J＝7.5,3.7,1.2Hz,1H),7.49–7.43(m,1H),7.43–7.39(m,2H),7.29–7.19(m,2H),7.15(td,J＝7.4,1.4Hz,1H),6.38(d,J＝2.3Hz,4H),6.21(t,J＝2.3Hz,2H),3.59(s,12H),1.70–1.58(m,4H),1.53(s,2H),1.42(s,2H),1.20–1.12(m,2H),1.08–0.93(m,10H),0.64–0.51(m,2H).13C NMR(101MHz,CDCl3)δ159.60,145.88(d,J＝31.6Hz),143.74,141.24,138.97(d,J＝5.6Hz),136.26(d,J＝18.4Hz),134.57(d,J＝6.0Hz),132.82,129.48,127.53,126.39,125.87,108.92,98.80,55.10,34.24(d,J＝14.7Hz),30.57(d,J＝16.5Hz),29.18(d,J＝11.9Hz),27.21(d,J＝11.3Hz),27.11(d,J＝7.9Hz),26.28.31P NMR(162MHz,CDCl3)δ-10.06.
(48)2-二环己基膦基-2',6'-二(2-萘基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，2-溴萘99.4mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品108.7mg白色固体，收率90％。1H NMR(400MHz,CDCl3)δ7.76–7.64(m,6H),7.60–7.52(m,5H),7.49(ddd,J＝7.5,3.7,1.1Hz,1H),7.42–7.31(m,6H),7.19–7.11(m,2H),7.11–7.04(m,1H),1.56(d,J＝11.6Hz,2H),1.47(d,J＝12.4Hz,2H),1.36(d,J＝10.6Hz,2H),1.13–0.94(m,6H),0.90–0.63(m,8H),0.42–0.30(m,2H).13C NMR(101MHz,CDCl3)δ145.92(d,J＝30.7Hz),141.62(d,J＝1.7Hz),139.64,139.48(d,J＝5.5Hz),135.89(d,J＝19.1Hz),134.65(d,J＝6.2Hz),133.06,132.86(d,J＝2.8Hz),131.82,130.07,129.57,128.80,128.00,127.77,127.26,126.64,126.47,126.43,125.70,125.61,33.98(d,J＝15.0Hz),30.58(d,J＝15.9Hz),29.15(d,J＝12.2Hz),27.14(d,J＝11.5Hz),27.00(d,J＝8.8Hz),26.13.31P NMR(162MHz,CDCl3)δ-9.30.
(49)2-环己基膦基-2',6'-二(3-呋喃基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3-溴呋喃70.5mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品66.2mg无色粘稠物，气相色谱纯度74％。
(50)2-环己基膦基-2',6'-二(3-噻吩基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，3-溴噻吩78.3mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品51.4mg浅黄色粘稠物，气相色谱纯度62％。
(51)2-环己基膦基-2',6'-二(4-(2-甲基)吡啶基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-溴-2-甲基吡啶82.6mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝60:1洗脱，真空干燥后得产品53.4mg白色固体，气相色谱纯度78％。
(52)2-环己基膦基-2',6'-二(6-喹啉基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，6-溴喹啉99.8mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝80:1洗脱，真空干燥后得产品66.5mg白色固体，气相色谱纯度83％。
(53)2-二环己基膦基-2',6'-二(4-(N-甲基)吲哚基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦基联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体2.5mg(原料摩尔数的2.5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，4-溴N-甲基吲哚100.8mg(0.48mmol)。140℃搅拌36小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品116.7mg白色固体，收率96％。1H NMR(400MHz,CDCl3)δ7.51–7.41(m,6H),7.17(d,J＝7.6Hz,1H),7.15–7.07(m,3H),7.06–7.01(m,3H),6.95(d,J＝3.0Hz,2H),6.34(d,J＝3.0Hz,2H),3.70(s,6H),1.65–1.58(m,2H),1.53(d,J＝12.9Hz,2H),1.46(d,J＝10.5Hz,2H),1.29(d,J＝10.8Hz,2H),1.08(t,J＝10.4Hz,6H),0.93(dd,J＝24.2,12.6Hz,4H),0.79–0.70(m,2H),0.67–0.57(m,2H).13C NMR(101MHz,CDCl3)δ147.12(d,J＝31.1Hz),142.59,139.59(d,J＝5.3Hz),135.77(d,J＝17.7Hz),135.27,134.82(d,J＝6.0Hz),133.64,132.39,129.56,128.59,127.96,127.19,126.40,125.69,124.60,122.87,107.72,101.09,33.82(d,J＝15.1Hz),32.69,30.94(d,J＝16.9Hz),28.91(d,J＝11.1Hz),27.30(d,J＝11.9Hz),27.02(d,J＝8.1Hz),26.27.31P NMR(162MHz,CDCl3)δ-10.00.
(54)2-环己基膦基-2'6'-二(5-苯并呋喃基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体5mg(原料摩尔数的5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，5-溴苯并呋喃94.6mg(0.48mmol)。140℃搅拌48小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品51.3mg白色固体，气相色谱纯度67％。
(55)2-环己基膦基-2'6'-二(5-苯并噻吩基)联苯的合成
25mL Schlenk管中，加入2-二环己基膦联苯(CyJohnPhos)70.1mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体5mg(原料摩尔数的5％)，叔丁醇锂48mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环1mL，5-溴苯并噻吩102.3mg(0.48mmol)。140℃搅拌24小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品49.2mg白色固体，气相色谱纯度76％。
(56)2-二苯基膦基-2'-苯基-1,1'-联萘的合成
25mL Schlenk管中，加入2-二苯基膦基-1,1'-联萘(H-MOP)44.0mg(0.2mmol)，(1,5-环辛二烯)氯铑(I)二聚体4.9mg(原料摩尔数的5％)，叔丁醇锂24mg(0.6mmol)，置换氩气三次，氩气保护下加入1,4-二氧六环0.5mL，溴苯314.0mg(2.0mmol)。150℃搅拌96小时，冷却至室温后减压蒸除溶剂，经200-300目硅胶层析柱分离，石油醚：乙酸乙酯＝100:1洗脱，真空干燥后得产品28.4mg白色固体，收率55％。1H NMR(400MHz,CDCl3)δ8.05(d,J＝8.5Hz,1H),7.91(d,J＝8.1Hz,1H),7.85(d,J＝8.1Hz,1H),7.74(d,J＝8.5Hz,1H),7.66(d,J＝8.5Hz,1H),7.49(ddd,J＝8.1,6.7,1.2Hz,1H),7.43(d,J＝8.3Hz,1H),7.38–7.29(m,2H),7.21(dd,J＝8.5,2.7Hz,1H),7.20–6.84(m,14H),6.76(d,J＝8.4Hz,1H),6.66–6.50(m,2H).13C NMR(101MHz,CDCl3)δ144.69(d,J＝34.6Hz),141.84,139.58(d,J＝2.8Hz),138.14(d,J＝13.1Hz),137.52(d,J＝14.6Hz),135.21(d,J＝10.9Hz),134.91(d,J＝8.1 Hz),134.48(d,J＝7.7 Hz),133.85(d,J＝21.3 Hz),133.41(d,J＝2.0 Hz),133.07(d,J＝0.9 Hz),132.44,132.42,132.27,130.69(d,J＝2.2 Hz),129.40(d,J＝1.0 Hz),128.38(d,J＝2.5 Hz),128.28,128.05,128.01,127.98,127.94,127.93,127.89,127.78,127.64(d,J＝2.6 Hz),127.47,127.24(d,J＝2.1 Hz),126.64,126.33,125.89,125.46.31P NMR(162 MHz,CDCl3)δ-14.42.