CN114702445B - 一种三齿氮配体及其合成方法与用途 - Google Patents

一种三齿氮配体及其合成方法与用途 Download PDF

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CN114702445B
CN114702445B CN202210220795.1A CN202210220795A CN114702445B CN 114702445 B CN114702445 B CN 114702445B CN 202210220795 A CN202210220795 A CN 202210220795A CN 114702445 B CN114702445 B CN 114702445B
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刘心元
王福利
杨昌江
李忠良
顾强帅
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Southern University of Science and Technology
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Abstract

本发明属于有机化学配体领域，公开了一种三齿氮配体，其具有通式Ⅰ的结构：其中，R1选自烷基、苯基、苄基且R2为氢，或者R1、R2＝‑(CH2)4‑；R3为喹啉基、异喹啉基或者R5选自氢、烷基、烷氧基、苄基、Ph2CH‑、卤素、三氟甲基、多环芳香烃基、取代苯基；R4为甲基或乙基。本发明还公开了三齿氮配体的合成方法与用途。本发明将酰胺基、吡啶基以及三级烷基胺组装在同一配体中，开发出一类新型的三齿NNN配体，该配体不仅能广泛应用于三级烷基氯代烃与末端炔烃的不对称交叉偶联反应，也对发展新型的催化体系解决其它类型自由基不对称反应具有重要意义。

Description

一种三齿氮配体及其合成方法与用途
技术领域
本发明属于有机化学配体领域，具体是一种三齿氮配体及其合成方法与用途。
背景技术
三齿配体在配位化学领域占有非常重要的地位。目前，已在合成化学、催化化学、材料化学、化学生物学等领域获得广泛的应用。由于含氮配体稳定性好，原料来源广泛，可以和众多金属形成配位作用等原因，NNN三齿配体已成为三齿配体最重要的分支之一。近年来，随着手性化学的蓬勃发展很多含氮手性配体被开发出来，与过渡金属络合的含氮手性配体在不对称催化反应中发挥越来越重要的作用。
在不对称催化的发展过程中，设计和合成新的手性配体一直是人们所关注的热点。近年来随着自由基不对称化学的发展，亟需开发不同骨架类型的手性配体来有效地调控自由基中间体的立体选择性控制。在众多配体结构单元中，酰胺基在自然界中广泛存在，是配位化学的一个重要结构单元。吡啶基可以和多种过渡金属形成配合物，早已受到化学家的关注。将酰胺基、吡啶基以及三级烷基胺组装在同一配体中，可以作为一类新型三齿NNN配体应用于催化反应中。另外将环己二胺手性骨架，不同类型氨基酸衍生物骨架引入到配体中，为催化反应提供特定的手性环境，从而诱导出高的对映体选择性。
发明内容
本发明的目的是提供一种基于酰胺基、吡啶基、三级烷基胺组装在一起的，骨架新颖的手性三齿氮配体。
本发明的另一目的是提供该三齿氮配体的合成方法。
本发明的另一目的是提供该三齿氮配体的用途。
为达到上述目的之一，本发明采用以下技术方案：
一种三齿氮配体，其具有通式Ⅰ的结构：
其中，R1选自烷基、苯基、苄基且R2为氢，或者R1、R2＝-(CH2)4-；
R3为喹啉基、异喹啉基或者
R5选自氢、烷基、烷氧基、苄基、Ph2CH-、卤素、三氟甲基、多环芳香烃基、取代苯基；
R4为甲基或乙基。
进一步地，所述R1选自(C1～C4)烷基、苯基、苄基且R2为氢，或者R1、R2＝-(CH2)4-。
进一步地，所述R1选自甲基、乙基、异丙基、叔丁基、苯基、苄基且R2为氢，或者R1、R2＝-(CH2)4-。
进一步地，所述R3为喹啉基、异喹啉基或者
R5选自氢、(C1～C4)烷基、(C1～C4)烷氧基、苄基、Ph2CH-、卤素、三氟甲基、多环芳香烃基、取代苯基。
进一步地，所述R3为喹啉基、异喹啉基或者
R5选自氢、(C1～C4)烷基、(C1～C4)烷氧基、Ph2CH-、卤素、三氟甲基、多环芳香烃基、取代苯基。
进一步地，所述R3为喹啉基、异喹啉基或者
R5选自氢、(C1～C4)烷基、(C1～C4)烷氧基、苄基、Ph2CH-、卤素、三氟甲基、萘基、蒽基、菲基、芘基、取代苯基。
进一步地，所述R3为喹啉基、异喹啉基或者
R5选自氢、甲基、乙基、异丙基、叔丁基、甲氧基、苄基、Ph2CH-、氟、氯、溴、三氟甲基、萘基、蒽基、菲基、芘基、取代苯基。
进一步地，所述取代苯基为
R6选自氢、烷基、苯基、烷基或苯基取代的苯基、多环芳香烃基、9-苯基蒽基，m为1～6。
进一步地，所述取代苯基为
R6选自氢、(C1～C4)烷基、苯基、(C1～C4)烷基或苯基取代的苯基、多环芳香烃基、9-苯基蒽基。
进一步地，所述取代苯基为
R6选自氢、(C1～C4)烷基、苯基、4-叔丁基苯基、3,5-二叔丁基苯基、3,5-二苯基苯基、多环芳香烃基、9-苯基蒽基。
进一步地，所述取代苯基为
R6选自氢、(C1～C4)烷基、苯基、4-叔丁基苯基、3,5-二叔丁基苯基、3,5-二苯基苯基、萘基、蒽基、菲基、9-苯基蒽基。
进一步地，所述取代苯基为
R6选自氢、叔丁基、苯基、4-叔丁基苯基、3,5-二叔丁基苯基、3,5-二苯基苯基、萘基、蒽基、菲基、9-苯基蒽基。
进一步地，所述m为1或2。
进一步地，所述R5为取代苯基时，取代的位置为
进一步地，所述R4为甲基。
进一步地，三齿氮配体选自以下化合物：
一种上述的三齿氮配体的制备方法，包括以下步骤：在EDCI和DMAP存在下，化合物S1和化合物S2反应如下
其中，R1选自烷基、苯基、苄基且R2为氢，或者R1、R2＝-(CH2)4-；
R3为喹啉基、异喹啉基或者
R5选自氢、烷基、烷氧基、苄基、Ph2CH-、卤素、三氟甲基；
R4为甲基或乙基。
进一步地，化合物S1、化合物S2、EDCI和DMAP的摩尔比为(1～2)：1：(2～6)：(1.5～3)；所述反应以二氯甲烷为溶剂；所述反应的温度为20℃以上，所述反应的时间至少是24h。
一种上述的三齿氮配体的制备方法，包括以下步骤：
在EDCI和DMAP存在下，化合物S3和化合物S2反应得到S4；
化合物S4和化合物S5反应得到产物；
其中，R1、R2＝-(CH2)4-；
R5选自多环芳香烃基、取代苯基；
R4为甲基或乙基。
进一步地，化合物S3、化合物S2、EDCI和DMAP的摩尔比为(1～2)：1：(2～6)：(1.5～3)；所述反应以二氯甲烷为溶剂；所述反应的温度为20℃以上，所述反应的时间至少是24h。
进一步地，所述反应加入四三苯基膦钯作为催化剂，加入碳酸钾作为碱；化合物S4、化合物S5、碳酸钾的摩尔比为1：(1～2):(2～4)；四三苯基膦钯的用量是4～12mol％；所述反应以四氢呋喃为溶剂；所述反应的温度为80～120℃，所述反应的时间是24～72h。
三齿氮配体在三级烷基氯代烃与末端炔烃的自由基不对称Sonogashira交叉偶联反应中的应用。
本文所用的“烷基”指饱和脂肪族烃基团，其为包含1至20个碳原子的直链或支链基团，优选含有1至12个碳原子的烷基，更优选含有1至6个碳原子的烷基。烷基基团的实例包括甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、戊基、2-戊基、异戊基、新戊基、己基、2-己基、3-己基、3-甲基戊基。
本文所用的“烷氧基”指-O-(烷基)和-O-(环烷基)，其中烷基、环烷基的定义如本文所述，烷氧基的非限制性实例包括：甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、仲丁氧基、叔丁氧基、戊氧基、2-戊氧基、异戊氧基、新戊氧基、己氧基、2-己氧基、3-己氧基、3-甲基戊氧基、环丙氧基、环丁氧基、环戊氧基、环己氧基。烷氧基基团通常具有通过氧桥连接的1至7个碳原子。烷氧基还包括取代烷氧基。烷氧基可任选被卤素取代一次或多次。
本文所用的“卤素”指氟、氯、溴和碘。
本文所用的“三氟甲基”指-CF3。
本文所用的“苄基”指PhCH2-。
本文所述“取代苯基”或“取代的苯基”的“取代”可以是单取代，也可以是多取代，还可以是没有取代基(即全部为氢原子)；“取代苯基”或“取代的苯基”包括：(1)苯环有一个非氢取代基；(2)苯环有两个及两个以上相同或不同的非氢取代基；(3)苯环上全部为氢原子，没有取代基。取代的位置可以是苯环2、3、4、5、6的任意位置。
本文所述“多环芳香烃基”由不包含杂环或取代基的芳香环所组成的芳香族碳氢化合物减少一个氢原子后所形成的取代基，包括萘基、蒽基、菲基、芘基、并四苯基、基、三亚苯基、并五苯基等。
“萘基”指包括1-萘基和2-萘基。
“蒽基”指包括1-蒽基、2-蒽基和9-蒽基。
“菲基”指包括1-菲基、2-菲基、3-菲基、4-菲基和9-菲基。
“芘基”指包括1-芘基、2-芘基、4-芘基和5-芘基。
“9-苯基蒽基”指
“异喹啉基”指包括1-异喹啉基、3-异喹啉基、4-异喹啉基、5-异喹啉基、6-异喹啉基、7-异喹啉基和8-异喹啉基。
“喹啉基”指包括2-喹啉基、3-喹啉基、4-喹啉基、5-喹啉基、6-喹啉基、7-喹啉基和8-喹啉基。
EDCI指1-乙基-3-(3-二甲基氨基丙基)碳二亚胺，DMAP指4-二甲氨基吡啶。
本发明具有以下有益效果：
本发明将酰胺基、吡啶基以及三级烷基胺组装在同一配体中，开发出一类新型的三齿NNN配体，并成功应用于不对称催化反应中。这类新型的手性配体具有丰富多变的结构，配体上吡啶环上不同电子效应和位阻效应的取代基的引入可以调控反应的活性和对映选择性；另外一个突出的优势在于将环己二胺手性骨架、不同类型氨基酸衍生物引入到配体中，不同类型的手性骨架为不同类型的催化反应提供独特的手性环境，从而诱导优秀的对映体选择性。本发明的配体不仅能广泛应用于三级烷基氯代烃与末端炔烃的不对称交叉偶联反应，也对发展新型的催化体系解决其它类型自由基不对称反应具有重要意义。
具体实施方式
除非另有说明，化学品均购自商业化产品并且不经进一步纯化。实验中使用的二氯甲烷等溶剂均为无水溶剂。薄层色谱分析(TLC)使用60F254硅胶板。硅胶柱层析使用青岛海洋硅胶(粒径0.040-0.063mm)。TLC显色采用UV光(254nm)或碘。NMR图谱使用BrukerDPX400核磁共振仪表征，1HNMR为400MHz，溶剂为氘代氯仿，以四甲基硅烷(TMS)为内标。化学位移的单位是ppm，耦合常数的单位是Hz。在1HNMR中，δ表示化学位移，s表示单峰，d表示双峰，t表示三重峰，q表示四重峰，p表示五重峰，m表示多重峰，br表示宽峰。
实施例1
向化合物S1(10～15mmol，优选12mmol)和化合物S2(10mol)的50mL二氯甲烷溶液中加入EDCI(20～60mmol，优选30mmol)和DMAP(15～30mmol，优选20mmol)。反应在室温下搅拌24小时，加入水淬灭。分离有机层，干燥，过滤并真空浓缩。由此获得的残余物通过硅胶柱纯化，得到产物(60～80％收率)。
按照以上方法合成化合物1～19。
1H NMR(400MHz,CDCl3)δ8.60(d,J＝2.2Hz,1H),8.16(s,1H),8.06(d,J＝8.3Hz,1H),7.94(dd,J＝8.4,2.3Hz,1H),3.81–3.68(m,1H),2.54–2.37(m,2H),2.24(s,6H),1.94–1.77(m,2H),1.75–1.63(m,1H),1.45–1.11(m,4H)。
实施例2
1H NMR(400MHz,CDCl3)δ8.93–8.80(m,1H),8.42–8.23(m,2H),8.21–8.03(m,1H),3.89–3.70(m,1H),2.55–2.45(m,2H),2.27(s,6H),1.96–1.82(m,2H),1.78–1.68(m,1H),1.40–1.15(m,4H)。
19F NMR(376MHz,CDCl3)δ-62.50。
实施例3
1H NMR(400MHz,CDCl3)δ8.83(d,J＝2.0Hz,1H),8.41(d,J＝2.0Hz,1H),8.36(d,J＝6.8Hz,1H),7.75–7.51(m,4H),3.70(tdd,J＝10.8,6.6,4.0Hz,1H),2.50–2.32(m,2H),2.28(s,6H),1.91–1.73(m,2H),1.71–1.60(m,1H),1.41–1.14(m,4H)。
实施例4
1H NMR(400MHz,CDCl3)δ8.71(dd,J＝5.5,3.4Hz,1H),8.56(d,J＝7.5Hz,1H),8.30(d,J＝6.4Hz,1H),8.05(dd,J＝7.5,1.5Hz,1H),7.89(ddd,J＝5.2,3.4,1.5Hz,1H),7.71(dd,J＝5.5,3.5Hz,2H),3.60–3.43(m,1H),2.35(dt,J＝9.8,7.5Hz,1H),2.30(s,6H),1.99–1.80(m,2H),1.76–1.60(m,1H),1.50–1.22(m,4H)。
实施例5
1H NMR(400MHz,CDCl3)δ8.51(d,J＝7.5Hz,1H),8.26(ddd,J＝15.0,7.4,1.5Hz,2H),8.20(s,1H),7.94–7.83(m,2H),7.57(td,J＝7.5,1.7Hz,1H),3.42(dt,J＝9.8,7.6Hz,1H),2.36(dt,J＝9.8,7.5Hz,1H),2.29(s,6H),2.10(dt,J＝7.6,5.6Hz,1H),1.76–1.59(m,3H),1.55–1.21(m,4H)。
实施例6
1H NMR(400MHz,CDCl3)δ8.79(dd,J＝8.1,1.3Hz,1H),8.38(d,J＝6.8Hz,1H),8.01(dd,J＝7.9,5.0Hz,1H),7.57(td,J＝8.1,1.3Hz,1H),3.39(dt,J＝9.8,7.6Hz,1H),2.37–2.30(m,1H),2.27(s,6H),2.06(dt,J＝7.8,5.6Hz,1H),1.75–1.56(m,4H),1.50–1.28(m,3H)。
实施例7
1H NMR(400MHz,CDCl3)δ8.96(d,J＝1.2Hz,1H),8.33(br,1H),8.09(d,J＝8.0Hz,1H),7.56(dd,J＝8.1,1.3Hz,1H),3.44–3.33(m,1H),2.37–2.29(m,1H),2.27(s,6H),2.11–2.01(m,1H),1.71–1.45(m,4H),1.50–1.25(m,3H)。
实施例8
1H NMR(400MHz,CDCl3)δ8.60(d,J＝5.0Hz,1H),8.18(br,1H),7.51(dd,J＝5.0,1.0Hz,1H),7.36(d,J＝1.1Hz,1H),3.79(s,3H),3.36–3.11(m,1H),2.74–2.48(m,1H),2.37–2.32(m,1H),2.29(s,6H),1.73–1.63(m,3H),1.64–1.47(m,3H),1.40–1.33(m,1H)。
实施例9
1H NMR(400MHz,CDCl3)δ8.78(d,J＝5.0Hz,1H),8.35(d,J＝6.8Hz,1H),8.19(d,J＝1.1Hz,1H),7.85(dd,J＝5.1,1.0Hz,1H),3.34–3.21(m,1H),2.68–2.52(m,1H),2.41–2.32(m,1H),2.29(s,6H),1.75–1.58(m,4H),1.50–1.22(m,3H)。
实施例10
1H NMR(400MHz,CDCl3)δ8.37(br,1H),7.84(dd,J＝7.9,1.1Hz,1H),7.69(t,J＝8.0Hz,1H),7.34(dd,J＝7.9,1.0Hz,1H),3.48(dt,J＝10.0,7.6Hz,1H),2.55(s,6H),2.54–2.49(m,1H),2.27(s,6H),2.01(dt,J＝7.6,5.6Hz,1H),1.74–1.38(m,7H)。
实施例11
1H NMR(400MHz,CDCl3)δ8.32(br,1H),7.87(dd,J＝8.0,1.1Hz,1H),7.63(t,J＝8.0Hz,1H),7.43(dd,J＝8.0,1.1Hz,1H),3.48–3.20(m,1H),2.76(q,J＝6.7Hz,2H),2.38–2.29(m,1H),2.27(s,6H),2.13–2.01(m,1H),1.77–1.57(m,4H),1.55–1.36(m,3H),1.17(t,J＝6.7Hz,3H)。
实施例12
1H NMR(400MHz,CDCl3)δ8.40(br,1H),7.82(dd,J＝7.9,1.1Hz,1H),7.69(t,J＝8.0Hz,1H),7.45(dd,J＝8.0,1.1Hz,1H),3.52–3.42(m,1H),3.00–2.89(m,1H),2.60–2.48(m,1H),2.27(s,6H),2.08–1.98(m,1H),1.75–1.39(m,7H),1.27(d,J＝6.4Hz,6H)。
实施例13
1H NMR(400MHz,CDCl3)δ8.29(br,1H),7.93(dd,J＝7.9,1.1Hz,1H),7.73(t,J＝8.0Hz,1H),7.49(dd,J＝8.0,1.1Hz,1H),3.31–3.12(m,1H),2.64–2.51(m,1H),2.39–2.34(m,1H),2.30(s,6H),1.74–1.40(m,7H),1.38(s,9H)。
实施例14
1H NMR(400MHz,CDCl3)δ8.43(br,1H),8.02(dd,J＝8.1,1.2Hz,1H),7.96(td,J＝7.9,4.8Hz,1H),7.25–7.14(m,1H),3.35–3.21(m,1H),2.65–2.52(m,1H),2.35–2.23(m,7H),1.75–1.32(m,7H)。
实施例15
1H NMR(400MHz,CDCl3)δ8.40(br,1H),8.11(dd,J＝7.9,1.1Hz,1H),7.85(t,J＝8.0Hz,1H),7.74(dd,J＝8.0,1.1Hz,1H),3.39–3.19(m,1H),2.67–2.53(m,1H),2.33–2.20(m,7H),1.73–1.58(m,4H),1.58–1.30(m,3H)。
实施例16
1H NMR(400MHz,CDCl3)δ8.54(br,1H),8.10(dd,J＝8.0,1.1Hz,1H),7.83(dd,J＝7.9,1.1Hz,1H),7.77(t,J＝8.0Hz,1H),3.42(dt,J＝10.0,7.6Hz,1H),2.51–2.47(m,1H),2.38(s,6H),1.68–1.25(m,7H)。
实施例17
1H NMR(400MHz,CDCl3)δ8.48(br,1H),8.33–8.25(m,1H),7.96(dd,J＝8.0,1.2Hz,1H),7.90(dd,J＝8.0,1.2Hz,1H),7.83(t,J＝8.0Hz,1H),7.54(t,J＝7.4Hz,1H),7.51–7.44(m,1H),3.40(dt,J＝10.0,7.6Hz,1H),2.58(s,6H),2.54–2.49(m,1H),2.21(s,6H),2.05(dt,J＝7.6,5.6Hz,1H),1.70–1.32(m,7H)。
实施例18
1H NMR(400MHz,CDCl3)δ8.30(br,1H),8.03(dd,J＝7.7,1.3Hz,1H),7.93–7.79(m,2H),7.21–7.13(m,1H),7.13–7.06(m,2H),7.03–6.93(m,2H),4.14(s,2H),3.60–3.43(m,1H),2.63–2.47(m,1H),2.29(s,6H),2.09–1.99(m,1H),1.72–1.31(m,7H)。
实施例19
1H NMR(400MHz,CDCl3)δ8.35(br,1H),8.08–8.00(m,1H),7.87–7.81(m,2H),7.44–7.39(m,4H),7.33–7.28(m,4H),7.24–7.15(m,2H),5.18(s,1H),3.53–3.34(m,1H),2.54–2.40(m,1H),2.13(s,6H),2.06–1.96(m,1H),1.73–1.30(m,7H)。
实施例20
步骤1：将化合物S3(12mmol)和化合物S2(10mol)的50mL二氯甲烷溶液中加入EDCI(30mmol)和DMAP(20mmol)。反应在室温下搅拌24小时，加入水淬灭。分离有机层，干燥，过滤并真空浓缩。由此获得的残余物通过硅胶柱纯化，得到产物S4(75％收率)。
步骤2：将中间体S4(5mmol)和化合物S5(5～8mmol,优选7mmol),四三苯基膦钯(0.20～0.60mmol,优选0.40mmol)，碳酸钾(10～20mmol,优选15mmol)置于100mL封管中，置换三次氩气，加入四氢呋喃30mL,去离子水5mL，随后在80～120℃(优选100℃)条件下搅拌24～72小时，通过TLC检测，直至化合物S4完全消失。后处理：冷却至室温，加入水和乙酸乙酯，分离有机层，干燥，过滤并真空浓缩。由此获得的残余物通过硅胶柱纯化，得到产物(50～80％收率)。
按照以上方法合成化合物20～37。
1H NMR(400MHz,CDCl3)δ8.79(d,J＝2.4Hz,1H),8.31(s,1H),8.24(d,J＝8.2Hz,1H),8.00(dd,J＝8.4,2.2Hz,1H),7.60(d,J＝7.6Hz,2H),7.53–7.37(m,3H),3.98–3.77(m,1H),2.66–2.39(m,2H),2.34(s,6H),2.02–1.65(m,3H),1.45–1.12(m,4H)。
实施例21
1H NMR(400MHz,CDCl3)δ8.79(d,J＝2.2Hz,1H),8.28(d,J＝6.8Hz,1H),8.23(d,J＝8.1Hz,1H),8.00(dd,J＝8.1,2.2Hz,1H),7.54(q,J＝8.5Hz,4H),3.85(tdd,J＝10.7,6.7,4.0Hz,1H),2.59–2.42(m,2H),2.30(s,6H),1.98–1.81(m,2H),1.76–1.67(m,1H),1.37(s,9H),1.32–1.08(m,4H)。
实施例22
1H NMR(400MHz,CDCl3)δ8.69(d,J＝2.0Hz,1H),8.30(d,J＝6.7Hz,1H),8.25(d,J＝8.0Hz,1H),8.08(dd,J＝8.0,2.2Hz,1H),7.58–7.51(m,3H),3.79(tdd,J＝10.6,6.8,4.0Hz,1H),2.54–2.40(m,2H),2.35(s,6H),1.99–1.83(m,2H),1.73–1.64(m,1H),1.35(s,9H),1.28–1.06(m,4H)。
实施例23
1H NMR(400MHz,CDCl3)δ8.92(d,J＝1.3Hz,1H),8.38(s,1H),8.28(dd,J＝8.0,1.2Hz,1H),8.07(d,J＝8.0Hz,1H),7.93–7.84(m,2H),7.74–7.67(m,2H),7.60–7.55(m,2H),7.53–7.46(m,2H),7.43–7.33(m,1H),3.93–3.72(m,1H),2.62–2.32(m,2H),2.31(s,6H),2.06–1.69(m,3H),1.41–1.15(m,4H)。
实施例24
1H NMR(400MHz,CDCl3)δ8.85(d,J＝1.3Hz,1H),8.43(s,1H),8.30(dd,J＝7.9,1.3Hz,1H),8.15–8.05(m,3H),8.02(dd,J＝7.5,1.5Hz,1H),7.93–7.83(m,3H),7.72–7.53(m,5H),3.99–3.78(m,1H),2.66–2.36(m,2H),2.37(s,6H),2.11–1.74(m,3H),1.47–1.12(m,4H)。
实施例25
1H NMR(400MHz,CDCl3)δ8.74(d,J＝2.0Hz,1H),8.31(dd,J＝8.1,1.3Hz,1H),8.26(s,1H),8.15–8.05(m,2H),8.05–7.92(m,3H),7.84(dd,J＝7.5,1.6Hz,1H),7.63(td,J＝7.5,1.5Hz,1H),7.55(td,J＝7.5,1.6Hz,1H),3.80(tdd,J＝10.6,6.7,4.0Hz,1H),2.53–2.40(m,2H),2.35(s,6H),1.92–1.75(m,2H),1.72–1.63(m,1H),1.36–1.13(m,4H)。
实施例26
1H NMR(400MHz,CDCl3)δ8.62(d,J＝1.6Hz,1H),8.45(s,1H),8.40–8.30(m,2H),8.26(d,J＝8.0,1H),8.09(d,J＝8.0Hz,1H),8.05–7.90(m,3H),7.60–7.50(m,2H),3.94–3.80(m,1H),2.62–2.53(m,2H),2.40(s,6H),2.07–1.75(m,3H),1.53–1.26(m,4H)。
实施例27
1H NMR(400MHz,CDCl3)δ8.93(s,1H),8.47(d,J＝8.2Hz,1H),8.27(d,J＝8.1Hz,1H),8.14(dd,J＝8.0,2.2Hz,1H),8.07(d,J＝1.8Hz,1H),8.00–7.83(m,3H),7.72(dd,J＝8.3,1.9Hz,1H),7.58–7.48(m,2H)，4.04–3.91(m,1H),2.67–2.55(m,2H),2.42(s,6H),2.08–1.80(m,3H),1.55–1.20(m,4H)。
实施例28
1H NMR(400MHz,CDCl3)δ8.62(d,J＝2.0Hz,1H),8.55(s,1H),8.44(d,J＝7.7Hz,2H),8.07(d,J＝8.5Hz,2H),7.92(dd,J＝7.9,2.1Hz,1H),7.59–7.44(m,4H),7.42–7.34(m,2H),4.01–3.86(m,1H),2.64–2.51(m,2H),2.35(s,6H),2.01–1.71(m,3H),1.50–1.23(m,4H)。
实施例29
1H NMR(400MHz,CDCl3)δ8.79(d,J＝1.3Hz,1H),8.45(d,J＝7.5Hz,1H),8.39(s,1H),8.33–8.22(m,2H),8.16–8.10(m,3H),8.09–8.01(m,4H),7.96(d,J＝7.5Hz,1H),3.89–3.76(m,1H),2.60–2.41(m,2H),2.40(s,6H),2.06–1.79(m,3H),1.55–1.27(m,4H)。
实施例30
1H NMR(400MHz,CDCl3)δ8.90(d,J＝2.1Hz,1H),8.33(d,J＝6.7Hz,1H),8.30(d,J＝8.1Hz,1H),8.12(dd,J＝8.1,2.3Hz,1H),7.86(t,J＝1.7Hz,1H),7.78(d,J＝1.7Hz,2H),7.72–7.66(m,4H),7.50(dd,J＝8.4,6.8Hz,4H),7.45–7.38(m,2H),3.93–3.78(m,1H),2.62–2.45(m,2H),2.31(s,6H),1.98–1.69(m,3H),1.46–1.19(m,4H)。
实施例31
1H NMR(400MHz,CDCl3)δ8.78(d,J＝1.8Hz,1H),8.45(s,1H),8.35(d,J＝7.4,1.6Hz,2H),8.25(dd,J＝7.9,1.3Hz,1H),8.16(dd,J＝7.4,1.6Hz,2H),8.07(d,J＝8.0Hz,1H),8.01–7.89(m,7H),7.77(t,J＝7.5Hz,2H),7.56(t,J＝7.5,1.6Hz,2H),7.43(t,J＝7.5,1.6Hz,2H),3.90–3.70(m,1H),2.59–2.41(m,2H),2.36(s,6H),1.92–1.63(m,3H),1.48–1.24(m,4H)。
实施例32
1H NMR(400MHz,CDCl3)δ8.85(d,J＝1.6Hz,1H),8.39(s,1H),8.33(dd,J＝8.0,1.2Hz,1H),8.08(d,J＝8.1Hz,1H),7.94–7.86(m,3H),7.55(s,2H),7.49(s,4H),4.03–3.81(m,1H),2.62–2.46(m,2H),2.40(s,6H),2.07–1.72(m,3H),1.43(s,18H),1.35(s,18H),1.30–1.12(m,4H)。
实施例33
1H NMR(400MHz,CDCl3)δ8.90(dd,J＝2.2,0.8Hz,1H),8.34(d,J＝6.6Hz,1H),8.29(dd,J＝8.0,0.8Hz,1H),8.11(dd,J＝8.1,2.3Hz,1H),7.86(t,J＝1.6Hz,1H),7.76(d,J＝1.7Hz,2H),7.67–7.58(m,4H),7.56–7.49(m,4H),3.94–3.75(m,1H),2.64–2.43(m,2H),2.31(s,6H),2.04–1.62(m,3H),1.39(s,18H),1.34–1.16(m,4H)。
实施例34
1H NMR(400MHz,CDCl3)δ8.87(d,J＝1.8Hz,1H),8.41(dd,J＝8.1,1.3Hz,1H),8.35(s,1H),8.22(dd,J＝7.3,1.6Hz,4H),8.15(s,3H),8.11–8.06(m,5H),7.68–7.62(m,4H),7.61–7.49(m,13H),7.42–7.35(m,2H),3.90–3.62(m,1H),2.65–2.48(m,2H),2.43(s,6H),2.02–1.57(m,3H),1.30–1.20(m,4H)。
实施例35
1H NMR(400MHz,CDCl3)δ8.75(d,J＝1.2Hz,1H),8.53(s,2H),8.42(s,1H),8.39(dd,J＝8.1,1.3Hz,1H),8.20–8.05(m,12H),7.65–7.56(m,4H),7.53–7.41(m,4H),3.83–3.55(m,1H),2.73–2.46(m,2H),2.49(s,6H),2.13–1.67(m,3H),1.35–1.25(m,4H)。
实施例36
1H NMR(400MHz,CDCl3)δ8.93(d,J＝1.3Hz,1H),8.78(dd,J＝7.4,1.6Hz,2H),8.54(dd,J＝7.3,1.7Hz,2H),8.38(s,1H),8.28(dd,J＝8.1,1.3Hz,1H),8.20–8.15(m,4H),8.02–7.87(m,6H),7.74–7.58(m,8H),3.72–3.45(m,1H),2.63–2.35(m,2H),2.39(s,6H),2.02–1.62(m,3H),1.33–1.20(m,4H)。
实施例37
1H NMR(400MHz,CDCl3)δ8.72(d,J＝1.6Hz,1H),8.24(dd,J＝8.1,1.3Hz,1H),8.09(d,J＝8.0Hz,1H),8.00(s,3H),7.98–7.95(m,2H),7.97(d,J＝2.0Hz,4H),7.91(t,J＝2.0Hz,2H),7.75–7.68(m,8H),7.52–7.45(m,8H),7.42–7.35(m,4H),3.90–3.76(m,1H),2.59–2.40(m,2H),2.38(s,6H),1.96–1.63(m,3H),1.42–1.15(m,4H)。
实施例38
将化合物S1(10～15mmol，优选12mmol)和化合物S6(10mol)的50mL二氯甲烷溶液中加入EDCI(20～60mmol，优选30mmol)和DMAP(15～30mmol，优选20mmol)。反应在室温下搅拌24小时，加入水淬灭。分离有机层，干燥，过滤并真空浓缩。由此获得的残余物通过硅胶柱纯化，得到产物(60～80％收率)。
按照以上方法合成化合物38～43。
1H NMR(400MHz,CDCl3)δ8.85(dd,J＝5.0,1.3Hz,1H),8.20(br,1H),8.13(dd,J＝7.9,1.1Hz,1H),7.92(ddd,J＝8.0,5.0,1.1Hz,1H),7.87(td,J＝8.0,1.3Hz,1H),3.88–3.74(m,1H),2.68(dd,J＝12.4,7.0Hz,1H),2.39(dd,J＝12.4,7.0Hz,1H),2.20(s,6H),1.27(d,J＝6.1Hz,3H)。
实施例39
1H NMR(400MHz,CDCl3)δ8.85(dd,J＝5.1,1.3Hz,1H),8.10(br,1H),8.04(dd,J＝8.1,1.1Hz,1H),7.98–7.90(m,1H),7.80(td,J＝8.0,1.3Hz,1H),3.70(dt,J＝10.6,2.9Hz,1H),2.93(dd,J＝12.4,2.9Hz,1H),2.48–2.36(m,1H),2.34(dd,J＝12.4,2.9Hz,1H),2.10(s,6H),0.90(d,J＝6.4Hz,6H)。
实施例40
1H NMR(400MHz,CDCl3)δ8.85(dd,J＝4.9,1.3Hz,1H),8.15(br,1H),8.00(dd,J＝8.1,1.1Hz,1H),7.95–7.90(m,1H),7.83(td,J＝7.9,1.3Hz,1H),3.53(t,J＝6.9Hz,1H),2.81(dd,J＝12.4,6.8Hz,1H),2.38–2.27(m,1H),2.15(s,6H),1.02(s,9H)。
实施例41
1H NMR(400MHz,CDCl3)δ8.66(d,J＝6.7Hz,1H),8.62–8.56(m,1H),8.15(dt,J＝7.8,1.1Hz,1H),7.82(td,J＝7.7,1.7Hz,1H),7.46–7.30(m,5H),7.26–7.22(m,1H),5.23–5.12(m,1H),2.84(dd,J＝12.7,9.9Hz,1H),2.57(dd,J＝12.7,5.3Hz,1H),2.32(s,6H)。
实施例42
1H NMR(400MHz,CDCl3)δ8.53(dt,J＝4.8,1.3Hz,1H),8.17(dt,J＝7.7,1.2Hz,1H),8.07(d,J＝8.3Hz,1H),7.83(td,J＝7.7,1.7Hz,1H),7.50–7.35(m,1H),7.32–7.12(m,5H),4.63–4.36(m,1H),3.17–2.89(m,2H),2.47(dd,J＝12.4,8.3Hz,1H),2.34(dd,J＝12.4,6.2Hz,1H),2.26(s,6H)。
实施例43
1H NMR(400MHz,CDCl3)δ8.85(dd,J＝2.3,0.8Hz,1H),8.28(dd,J＝8.1,0.8Hz,1H),8.11(dd,J＝8.2,2.1Hz,2H),7.86(t,J＝1.7Hz,1H),7.75(d,J＝1.7Hz,2H),7.67–7.60(m,4H),7.56–7.50(m,4H),7.34–7.26(m,4H),7.25–7.19(m,1H),4.51(ddt,J＝14.2,8.0,6.0Hz,1H),3.10(dd,J＝13.7,5.7Hz,1H),3.01(dd,J＝13.7,6.2Hz,1H),2.49(dd,J＝12.4,8.1Hz,1H),2.37(dd,J＝12.4,6.4Hz,1H),2.29(s,6H),1.40(s,18H)。
实施例44
将本发明的配体应用于三级烷基氯代烃与末端炔烃的自由基不对称交叉偶联反应。
向装有磁力搅拌棒、经烘箱干燥的Schlenk管中加入三氟甲磺酸铜(10mol％当量)、配体L(15mol％)、苯乙炔(1.5当量)、碳酸铯(3.0当量)，置换氩气三次，随后加入三氟甲苯(1.0mL)。然后在室温条件下反应36h。反应完成后(通过TLC监测)，滤出沉淀物并用溶剂洗涤，然后蒸发溶液并通过硅胶柱色谱纯化(石油醚/乙酸乙酯＝20/1)，以75％收率、86％ee得到产物。
产物的表征数据：为淡黄色固体,HPLC条件:Chiralcel IA(正己烷/异丙醇＝98/2,流速0.4mL/min,λ＝254nm),tR(minor)＝24.7min,tR(major)＝28.3min。
1H NMR(400MHz,CDCl3)δ8.41(s,1H),7.83–7.74(m,2H),7.64–7.56(m,2H),7.55–7.48(m,2H),7.44–7.35(m,5H),7.34–7.27(m,3H),7.14–7.05(m,1H),2.53(dq,J＝13.5,7.3Hz,1H),2.19(dq,J＝13.5,7.3Hz,1H),1.08(t,J＝7.3Hz,3H)。
13C NMR(100MHz,CDCl3)δ168.9,139.8,137.7,131.7,129.0,128.9,128.6,128.5,127.66,126.62,124.4,122.2,119.7,89.9,88.7,55.3,33.3,10.2。
HRMS(ESI)m/z精确质量C24H22NO[M+H]+340.1696,实测值340.1691。
反应结果如下表所示(L1表示实施例1的配体，以此类推)：
可见，本发明的配体可以和铜盐作为催化剂，用于末端炔烃和三级烷基氯代烃为不对称交叉偶联反应，构建全碳手性季碳中心，具有良好的收率和优异的对映选择性。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何属于本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求的保护范围为准。

Claims (4)

1.一种三齿氮配体，其选自以下化合物：
2.一种权利要求1所述的三齿氮配体的制备方法，其特征在于，包括以下步骤：在1-乙基-3-(3-二甲基氨基丙基)碳二亚胺和4-二甲氨基吡啶存在下，化合物S1和化合物S2反应如下
其中，R1、R2、R3、R4与权利要求1对应。
3.一种权利要求1所述的三齿氮配体的制备方法，其特征在于，包括以下步骤：
在1-乙基-3-(3-二甲基氨基丙基)碳二亚胺和4-二甲氨基吡啶存在下，化合物S3和化合物S2反应得到S4
化合物S4和化合物S5反应得到产物
其中，R4、R5与权利要求1对应。
4.权利要求1所述的三齿氮配体在三级烷基氯代烃与末端炔烃的自由基不对称Sonogashira交叉偶联反应中的应用。
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