CN114436996B - 一种β2-氨基酸衍生物的制备方法 - Google Patents

一种β2-氨基酸衍生物的制备方法 Download PDF

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CN114436996B
CN114436996B CN202111670491.7A CN202111670491A CN114436996B CN 114436996 B CN114436996 B CN 114436996B CN 202111670491 A CN202111670491 A CN 202111670491A CN 114436996 B CN114436996 B CN 114436996B
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CN114436996A (zh
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袁伟明
郑松林
胡媛媛
陈子敏
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Huazhong University of Science and Technology
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Abstract

本发明属于有机合成技术领域，更具体地，涉及一种β2‑氨基酸衍生物的制备方法。以α‑氨甲基硅、烯烃和芳基(或杂芳基)卤代物为原料，在特定的配体结构和溶剂存在条件下，在保护气体的保护、光照以及光催化剂/过渡金属催化剂的协同催化作用下，一步反应后分离提纯即可得到β2‑氨基酸衍生物，该制备方法简单，反应选择性好且底物普适性强，由此解决现有技术中β2‑氨基酸衍生物制备方法存在的步骤繁琐、反应条件苛刻、反应官能团兼容性较差、收率低等技术问题。

Description

一种β2-氨基酸衍生物的制备方法
技术领域
本发明属于有机合成技术领域，更具体地，涉及一种β2-氨基酸衍生物的制备方法。
背景技术
β2-氨基酸衍生物是一类非常重要的分子骨架，存在于许多生物活性分子和药物中。如专利CN 101198606A，WO 2005/092858 A2公开了一种β2-氨基酸衍生物具有ORL1受体拮抗剂活性，能够用于缓解和治疗各种疼痛以及其他各种中枢神经***疾病。在这些专利文献中，合成具有ORL1受体拮抗剂活性的β2-氨基酸衍生物至少需要4步反应，且平均收率只有15％，在这些反应中，需要用到强碱，官能团的兼容性较差，原子经济性和步骤经济性都较差且原料并非廉价易得的。进行药物结构优化筛选时，无法同时合成一系列该类型的β2-氨基酸衍生物，这使得药物研发的周期大大增加。
因此，开发一种可模块化、操作简便，官能团兼容性好，原子经济性和步骤经济性较高的新方法，用于该化合物分子骨架的合成是十分重要的。
发明内容
针对现有技术的缺陷，本发明提供了一种β2-氨基酸衍生物的制备方法，其以α-氨甲基硅、烯烃和芳基(或杂芳基)卤代物为原料，在特定的配体结构和溶剂存在条件下，在保护气体的保护、光照以及光催化剂/过渡金属催化剂的协同催化作用下，一步反应后分离提纯即可得到β2-氨基酸衍生物，该制备方法简单，反应选择性好且底物普适性强，由此解决现有技术中这类化合物制备方法存在的步骤繁琐、反应条件苛刻、反应官能团兼容性较差、收率低等技术问题。
为实现上述目的，本发明提供了一种β2-氨基酸衍生物的制备方法，其特征在于，在溶剂和配体存在条件下，以式(二)所示的α-氨甲基硅、式(三)所示的烯烃和式(四)所示的芳基卤代物或杂芳基卤代物为原料，在保护气体的保护、光照以及光催化剂/过渡金属催化剂的协同催化作用下，充分反应后经分离提纯得到式(一)所示的β2-氨基酸衍生物；反应式如下：
其中，R1、R2各自独立地选自下列之一：C1～C25的烷基、C3～C10的环烷基、C6～C20的芳基、C3～C20的杂芳基、C6～C20的取代芳基、C3～C20的取代杂芳基、C2～C10的烯基；或者
R1、R2与其相邻的氮原子一起形成3～7元环，除该氮原子外，所述3～7元环中包含或不包含额外的杂原子和/或环内或环外双键，所述杂原子为N、S或O，所述双键为一个或两个；且所述3～7元环上的碳原子被一个或多个各自独立地选自下列的取代基取代：H原子、C1～C25的烷基、C3～C10的环烷基、C6～C20的芳基、C3～C20的杂芳基、C6～C20的取代芳基、C3～C20的取代杂芳基或C2～C10的烯基；
R3、R4、R5各自独立地选自下列之一：C1～C10的烷基、C6～C20的芳基、C6～C20的取代芳基；
EWG选自C1-C50的吸电子基团；
Ar为C6～C30的芳基或C3～C30的芳杂基；
X选自卤素或拟卤化合物；
所述配体选自氮原子邻位有一个或多个取代基的联吡啶类双齿氮配体、1,10-菲罗啉类双齿氮配体、双噁唑啉类双齿氮配体、邻二胺双齿氮配体和邻二亚胺双齿氮配体。
优选地，所述R1、R2各自独立地选自C1～C10的烷基、C6-C10的芳基、C3-C10的杂芳基、C6-C10的取代芳基、C3-C10的取代杂芳基；所述R3、R4、R5各自独立选自下列之一：C1～C5的烷基、C6-C10芳基、C6-C10取代芳基。
优选地，所述EWG选自C1-C50的酯基、C1-C50的酰胺基或氰基。
优选地，所述Ar为C6～C20的芳基或C3～C20的芳杂基。
优选地，所述X选自溴、碘、氯、三氟甲磺酸酯、对甲苯磺酸酯和甲磺酸酯。
优选地，所述光催化剂为含金属元素的光催化剂或染料类有机光催化剂；所述过渡金属催化剂为NiCl2、Ni(dppf)Cl2、NiBr2、NiCl2·glyme和NiBr2·glyme中的一种或多种。
优选地，所述配体选自如式(五)、式(六)、式(七)、式(八)和式(九)中所示的结构式中的一种或多种：
其中，R6、R7、R8和R9各自独立地选自下列之一：氢原子、C1～C25的烷基、C6～C20的芳基、C3～C20的杂芳基、C6～C20的取代芳基、C3～C20的取代杂芳基、C2～C10的烯基、氟、氯、溴、氰基、乙酰基、醛基、酯基、乙酰氧基和C1～C5的烷氧基；
进一步优选地，R6、R7、R8和R9各自独立地选自C1～C6的烷基、C6～C10的取代芳基、乙酰基、酯基和C1～C5的烷氧基；
进一步优选地，所述配体选自如式(五)和式(六)中所示的结构中的一种或多种。
优选地，式(二)所示的α-氨甲基硅、式(三)所示的烯烃和式(四)所示的芳基卤代物或杂芳基卤代物的摩尔比为(1～10)：1：(1～10)。
优选地，所述溶剂为N-甲基吡咯烷酮、乙腈、1，4-二氧六环、甲苯、三氟甲苯、N,N’-二甲基甲酰胺和N,N’-二甲基乙酰胺中的一种或多种。
优选地，所述光照为可见光照射，进一步优选为蓝光照射。
总体而言，通过本发明所构思的以上技术方案与现有技术相比，具有以下有益效果：
(1)本发明提供的一种β2-氨基酸衍生物的制备方法，其以本发明所述的α-氨甲基硅，芳基(或杂芳基)卤代物和烯烃为底物，在特定结构的配体存在条件下，一步反应制备得到。反应条件温和，原料廉价易得，操作简单、安全，使用光催化绿色环保并且高效，反应选择性好，底物普适性广，官能团兼容性高以及反应的原子和步骤经济性高等优点，可以作为含有β2-氨基酸衍生物的分子骨架合成的有效替代方法。
(2)本发明提出的制备方法可以通过改变α-氨甲基硅，芳基(或杂芳基)卤代物和烯烃的取代基，可以合成不同取代基的β2-氨基酸衍生物，能够应用于该类化合物库的快速构建，便于该类具有药物活性结构的β2-氨基酸衍生物的合成，改变原料的取代基便得到结构丰富多样的此类产物，适合模块化合成。
(3)本发明提出的制备方法使用可见光/过渡金属协同催化策略可以一步快速合成β2-氨基酸衍生物，该方法官能团兼容性好，原料廉价易得，无需额外的碱且反应呈氧化还原中性特征，具有优异的原子和步骤经济性。
(4)本发明提出的制备方法中反应原料廉价易得，α-氨甲基硅底物易制备，很多芳(杂芳)基卤代物和烯烃商业可得。
(5)本发明通过对反应底物、配体结构等原料进行筛选，优选实施例中合成得到的β2-氨基酸衍生物的收率可高达近90％。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明提供了一种β2-氨基酸衍生物的制备方法，在溶剂和配体存在条件下，以式(二)所示的α-氨甲基硅、式(三)所示的烯烃和式(四)所示的芳基卤代物或杂芳基卤代物为原料，在保护气体的保护、光照条件以及光催化剂/过渡金属催化剂的协同催化作用下(“/”表示二者的混合物)，充分反应后经分离提纯得到式(一)所示的β2-氨基酸衍生物；反应式如下：
其中，R1、R2各自独立地选自下列之一：C1～C25的烷基、C3～C10的环烷基、C6～C20的芳基、C3～C20的杂芳基、C6～C20的取代芳基、C3～C20的取代杂芳基、C2～C10的烯基；一些实施例中，所述取代芳基或取代杂芳基的苯环上被单取代或多取代，其取代基各自独立地选自C1～C10的烷基、氟、氯、溴、氰基、乙酰基、醛基、酯基、乙酰氧基或C1～C5的烷氧基；或者：
R1、R2与其相邻的氮原子一起形成3～7元环，除该氮原子外，所述3～7元环中包含或不包含额外的杂原子和/或双键，所述杂原子为N、S或O，所述双键为一个或两个；且所述3～7元环上的碳原子被一个或多个各自独立地选自下列的取代基取代：H原子、C1～C25的烷基、C3～C10的环烷基、C6～C20的芳基、C3～C20的杂芳基、C6～C20的取代芳基、C3～C20的取代杂芳基或C2～C10的烯基。一些实施例中，所述取代芳基或取代杂芳基的环上被单取代或多取代，其取代基各自独立地选自C1～C10的烷基、氟、氯、溴、氰基、乙酰基、醛基、酯基、乙酰氧基或C1～C5的烷氧基。优选实施例中，R1、R2各自独立地选自C1～C10的烷基、C6-C10的芳基、C3-C10的杂芳基、C6-C10的取代芳基、C3-C10的取代杂芳基。
R3、R4、R5各自独立地选自下列之一：C1～C10的烷基、C6～C20的芳基、C6～C20的取代芳基；一些实施例中，所述取代芳基的芳环上被单取代或多取代，其取代基各自独立选自C1～C10的烷基、氟、氯、溴、碘、氰基或C1～C5的烷氧基中的一种；优选实施例中，R3、R4、R5各自独立选自下列之一：C1～C5的烷基、C6-C10芳基、C6-C10取代芳基。
EWG(吸电子基团)选自C1-C50的吸电子基团；较佳实施例中，EWG(吸电子基团)选自C1-C50的酯基、C1-C50的酰胺基或氰基，更佳为C1-C30的酯基、C1-C30的酰胺基，进一步优选为C1-C10的酯基、C1-C10的酰胺基。
Ar为C6～C30的芳基或C3～C30的芳杂基环，一些实施例中，所述芳基或芳杂基的环上被单取代或多取代，其取代基各自独立选自C1～C10的烷基、芳基、芳杂基、卤素、氰基、酰基、醛基、酰胺基、酯基、酰氧基、取代胺基或C1～C5的烷氧基。优选实施例中，Ar为C6～C20的芳基或C3～C20的芳杂基环。一些实施例中，所述Ar芳基或芳杂基的环上被单取代或多取代，其取代基各自独立选自C1～C10的烷基、芳基、芳杂基、卤素、氰基、酰基、醛基、酰胺基、酯基、酰氧基、取代胺基或C1～C5的烷氧基。
X选自卤素或拟卤化合物；优选实施例中，所述X选自溴、碘、氯、三氟甲磺酸酯(OTf)、对甲苯磺酸酯(OTs)或甲磺酸酯(OMs)等拟卤化合物。
本发明式(二)所示的α-氨甲基硅包括但不限于1a(1-((trimethylsilyl)methyl)piperidine),1b(N-butyl-N-((trimethylsilyl)methyl)butan-1-amine),1c(methyl 4-(benzyl((trimethylsilyl)methyl)amino)butanoate),1d(4-(((tert-butyldimethylsilyl)oxy)methyl)-1-((trimethylsilyl)methyl)piperidine),1e(methyl 1-((trimethylsilyl)methyl)piperidine-4-carboxylate),1f(2-((trimethylsilyl)methyl)-1,2,3,4-tetrahydroisoquinoline),1g(N-phenyl-N-((trimethylsilyl)methyl)aniline),1h(N-benzyl-N-((trimethylsilyl)methyl)ethanamine),1i(1-((trimethylsi1k lyl)methyl)pyrrolidine),1j(4-((trimethylsilyl)methyl)morpholine),1k(tert-butyl 4-((trimethylsilyl)methyl)piperazine-1-carboxylate),1l((1-((trimethylsilyl)methyl)piperidin-4-yl)methylbenzoate)，1m(1'-((trimethylsilyl)methyl)-2H-spiro[benzofuran-3,4'-piperidine]),1n(1'-((trimethylsilyl)methyl)-2,3-dihydrospiro[indene-1,4'-piperidine])等。
本方法中式(三)所示的烯烃包括但不限于2a(丙烯酸苄酯)，2b(丙烯酸叔丁酯)，2c(丙烯酸烯丙酯)，2d(丙烯酰苯胺)，2e(丙烯酰苄胺)，2f(丙烯酰二甲胺),2g(丙烯酰二苄胺),2h(丙烯酰二苯胺),2i(N-methyl-N-phenylacrylamide),2j(1-morpholinoprop-2-en-1-one),2k(1-(azepan-1-yl)prop-2-en-1-one),2l(丙烯腈),2m(丙烯酸甲酯)等。
本方法中式(四)所示的芳基(或杂芳基)卤代物包括但不限于：3-1(碘苯)，3-2(对甲基碘苯)，3-3(间甲基碘苯)，3-4(邻甲基碘苯)，3-5(对甲氧基碘苯)，3-6(对苯基碘苯)，3-7(对碘苯甲腈)，3-8(对碘苯乙酮)，3-9(对碘乙酰苯酚)，3-10(对碘苯甲酸乙酯)，3-11(tert-butyl(4-iodophenoxy)dimethylsilane),3-12(对碘苯甲硫醚),3-13((4-iodophenyl)(morpholino)methanone),3-14(对氟碘苯),3-15(对氯碘苯),3-16(对三氟甲氧基碘苯),3-17(对溴苯乙烯),3-18(1-bromo-4-cyclopropylbenzene),3-19(对溴苯硼酸频那醇酯)，3-20((4-bromophenyl)trimethylsilane),3-21(2-溴萘),3-22(methyl 4-bromo-2-fluorobenzoate),3-23(4-((4-bromophenyl)sulfonyl)morpholine),3-24(N-benzyl-N-(4-iodophenyl)acetamide),3-25(tert-butyl3-bromo-9H-carbazole-9-carboxylate),3-26(2-bromodibenzo[b,d]thiophene),3-27(4-溴-2-甲氧基吡啶),3-28(5-溴-2-甲氧基嘧啶),3-29(5-iodo-1H-indole-1-carboxylate),3-30(5-溴苯并噻唑),3-31(1-碘-3,4-亚甲基二氧苯),3-32(6-溴喹啉),3-33(4-溴噻吩-2-甲酸甲酯),3-34(5-溴苯并呋喃)等。
优选实施例中，所述光催化剂为含金属元素的光催化剂或染料类有机光催化剂，包括但不限于Ir(ppy)2(bpy)PF6，Ru(bpy)3(PF6)2，Ir[dF(CF3)ppy]2(dtbbpy)PF6，fac-Ir(ppy)3，Ir[dF(CF3)ppy]2(bpy)PF6，Ir(ppy)2(dtbpy)PF6，Ir[dFppy]2(dtbbpy)PF6或4CzIPN。其中4CzIPN为最优可见光催化剂，其收率最高且价格低廉。
光催化剂/过渡金属催化剂中的“/”表示二者的混合物。本发明所述过渡金属催化剂用于和光催化剂协同催化本发明的合成反应，本方法中过渡金属催化剂包括但不限于：NiCl2，Ni(dppf)Cl2，NiBr2，NiCl2·glyme，NiBr2·glyme等，其中NiBr2·glyme为最优金属催化剂。
本发明所述配体用于与过渡金属催化剂配位，调控反应选择性，促进反应进行，配体的结构是该反应能够顺利发生的关键，本发明所述配体为氮原子邻位有一个或多个取代基的联吡啶类(bpy)、氮原子邻位有一个或多个取代基的1,10-菲罗啉类(1,10-phen)、氮原子邻位有一个或多个取代基的双噁唑啉类(BOX)、氮原子邻位有一个或多个取代基的邻二胺、氮原子邻位有一个或多个取代基的邻二亚胺等双齿氮配体。
一些实施例中，本发明采用配体的可选自如下式(五)、式(六)、式(七)、式(八)和式(九)所示的结构中的一种或多种：
其中，R6、R7、R8、R9各自独立地选自下列之一：氢原子、C1～C25的烷基、C6～C20的芳基、C3～C20的杂芳基、C6～C20的取代芳基、C3～C20的取代杂芳基、C2～C10的烯基、氟、氯、溴、氰基、乙酰基、醛基、酯基、乙酰氧基或C1～C5的烷氧基；较佳实施例中，R6、R7、R8和R9各自独立地选自C1～C6的烷基、C6～C10的取代芳基、酯基或C1～C5的烷氧基。
较佳实施例中，所述配体选自式(五)和/或式(六)所示的结构，包括但不限于6,6'-二甲基-2,2'-联吡啶(6,6'-di(Me)bpy)、6,6'-二甲氧基-2,2'-联吡啶(6,6'-di(OMe)bpy)、2,2'-联吡啶-6,6'-二甲酸二甲酯(6,6'-di(COOMe)bpy)、6-甲基-2,2'-联吡啶(6-Mebpy)、2,9-二甲基-1,10-菲罗啉((2,9-di(Me)phen))，其中最优配体为6,6'-二甲基-2,2'-联吡啶(6,6'-di(Me)bpy)，采用该配体时实验证明相同条件下其选择性最好，收率最高且价格便宜。
本发明采用催化剂剂量的光催化剂和过渡金属催化剂以实现合成反应。优选实施例中，过渡金属催化剂用量占式(四)的所示的芳基或杂芳基卤代物摩尔量的5％-15％，光催化剂用量占式(四)的所示的芳基或杂芳基卤代物摩尔量的0.5％-1.5％；配体用量占式(四)的所示的芳基或杂芳基卤代物摩尔量的5％-15％。
本发明制备方法中式(二)所示的α-氨甲基硅、式(三)所示的烯烃和式(四)的所示的芳基或杂芳基卤代物摩尔比为任意摩尔比均可得到式(一)所示的产物。一些实施例中，式(二)所示的α-氨甲基硅、式(三)所示的烯烃和式(四)所示的芳基卤代物或杂芳基卤代物的摩尔比为(1～10)：1：(1～10)。优选的摩尔比范围为(1～3)：1：(1～3)，进一步优选为1.5：1：1.5。
一些实施例中，所述溶剂为N,N’-二甲基甲酰胺(DMF)和N,N’-二甲基乙酰胺(DMAc)或N-甲基吡咯烷酮(NMP)中的一种或多种。本发明所述光照为可见光照射，优选实施例中其为蓝光照射。本发明合成反应的反应温度范围较宽，比如可以为-15℃-45℃。本发明所述保护气体为氮气或其它惰性气体(比如氩气)。本发明制备方法中，优选的反应时间为不少于2小时。
一些实施例中，本方法是将α-氨甲基硅，芳基(或杂芳基)卤代物和烯烃按一定比例加入到反应器中，再加入适量的光催化剂和金属催化剂、配体以及溶剂，氮气保护，在蓝光照射下室温反应一定时间，再通过萃取，干燥，提纯得到β2-氨基酸衍生物。此方法可以使用不同的α-氨甲基硅，芳基(或杂芳基)卤代物和烯烃来快速合成不同取代基的β2-氨基酸衍生物。此方法操作简单，原料廉价易得，反应条件温和，只需一步反应就能合成较为复杂的药物活性分子，能够用于快速构建含有此类药物活性分子骨架的化合物库。
以下为实施例：
实施例1
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-1(92mg,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物4(70mg，收率69％)。1H NMR(600MHz,CDCl3)δ7.33–7.26(m,3H),7.26–7.16(m,5H),7.13(d,J＝7.8Hz,2H),5.06–5.01(m,2H),3.03–2.97(m,1H),2.94–2.79(m,2H),2.68(t,J＝10.8Hz,1H),2.46–2.20(m,5H),1.53–1.45(m,4H),1.41–1.30(m,2H)ppm.13C NMR(151MHz,CDCl3)δ175.00,139.24,136.21,128.95,128.46,128.45,128.12,128.01,126.39,66.01,61.04,54.72,46.13,36.90,26.08,24.45ppm.IR:2933,1732,1454,1149,738,696cm-1.HRMS(ESI)for C22H28NO2 +[(M+H)+]:calculated 338.2115,found 338.2107。
实施例2
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-2(98mg,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物5(81mg，收率77％)。1H NMR(600MHz,CDCl3)δ7.29(d,J＝7.2Hz,3H),7.20(d,J＝6.8Hz,2H),7.04–7.01(m,4H),5.04(s,2H),2.97(dt,J＝13.9,6.9Hz,1H),2.86–2.76(m,2H),2.67(t,J＝10.9Hz,1H),2.42–2.36(m,3H),2.30–2.28(m,5H),1.54–1.42(m,4H),1.39–1.36(m,2H)ppm.13C NMR(151MHz,CDCl3)δ175.12,136.27,136.11,135.83,129.17,128.83,128.44,128.14,128.00,65.99,61.05,54.74,46.23,36.54,26.10,24.48,21.16ppm.IR:2932,1733,1515,1454,1149,733,696cm-1.HRMS(ESI)for C23H30NO2 +[(M+H)+]:calculated 352.2271,found 352.2259。
实施例3
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-3(98mg,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物6(75mg，收率71％)。1H NMR(600MHz,CDCl3)δ7.33–7.25(m,3H),7.21–7.17(m,2H),7.12(t,J＝7.5Hz,1H),7.00–6.93(m,3H),5.04(s,2H),3.04–2.96(m,1H),2.85(dd,J＝13.7,9.0Hz,1H),2.78(dd,J＝13.7,5.9Hz,1H),2.68(dd,J＝12.3,9.4Hz,1H),2.47–2.33(m,3H),2.31–2.19(m,5H),1.54–1.44(m,4H),1.39–1.35(m,2H)ppm.13C NMR(151MHz,CDCl3)δ175.10,139.20,137.97,136.27,129.74,128.46,128.36,128.08,128.00,127.14,125.97,65.97,61.13,54.74,46.15,36.85,26.13,24.49,21.49ppm.IR:2933,1733,1454,1149,734,696cm-1.HRMS(ESI)for C23H30NO2 +[(M+H)+]:calculated 352.2271,found352.2264.
实施例4
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-4(98mg,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物7(51mg，收率48％)。1H NMR(600MHz,CDCl3)δ7.33–7.26(m,3H),7.21–7.17(m,2H),7.13–7.03(m,4H),5.07–4.99(m,2H),3.01–2.95(m,1H),2.88–2.85(m,2H),2.72(dd,J＝12.4,9.2Hz,1H),2.49–2.35(m,3H),2.34–2.22(m,5H),1.52–1.45(m,4H),1.39–1.33(m,2H)ppm.13C NMR(151MHz,CDCl3)δ175.25,137.60,136.25,130.44,129.51,128.48,128.12,128.02,126.54,126.01,66.05,61.46,54.85,44.88,34.26,26.15,24.49,19.51ppm.IR:2932,1733,1454,1151,739,696cm-1.HRMS(ESI)for C23H30NO2 +[(M+H)+]:calculated352.2271,found 352.2260.
实施例5
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-5(0.11g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物8(70mg，收率63％)。1H NMR(400MHz,CDCl3)δ7.33–7.26(m,3H),7.23–7.18(m,2H),7.06–7.03(m,2H),6.78–6.76(m,2H),5.04(s,2H),3.77(s,3H),3.00–2.92(m,1H),2.87–2.74(m,2H),2.67(dd,J＝12.3,9.3Hz,1H),2.49–2.18(m,5H),1.52–1.47(m,4H),1.40–1.35(m,2H)ppm.13C NMR(151MHz,CDCl3)δ175.10,158.21,136.26,131.25,129.92,128.44,128.13,128.01,113.87,65.96,61.01,55.29,54.74,46.37,36.07,26.12,24.48ppm.IR:2933,1732,1512,1245,1149,1034,742,696cm-1.HRMS(ESI)for C23H30NO3 +[(M+H)+]:calculated368.2220,found 368.2206。
实施例6
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物9(109mg，收率88％)。1H NMR(400MHz,CDCl3)δ7.60–7.53(m,2H),7.49–7.38(m,4H),7.36–7.29(m,1H),7.28–7.23(m,3H),7.22–7.15(m,4H),5.05(d,J＝2.1Hz,2H),3.07–2.98(m,1H),2.97–2.82(m,2H),2.71(dd,J＝12.4,9.1Hz,1H),2.51–2.20(m,5H),1.56–1.46(m,4H),1.41–1.29(m,2H)ppm.13C NMR(151MHz,CDCl3)δ175.03,141.07,139.30,138.40,136.18,129.40,128.84,128.48,128.18,128.05,127.21,127.19,127.09,66.10,61.10,54.78,46.16,36.57,26.14,24.49ppm.IR:2932,1731,1486,1149,752,694cm-1.HRMS(ESI)for C28H32NO2 +[(M+H)+]:calculated 414.2428,found 414.2420.m.p.52.1℃–53.8℃。
实施例7
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-7(0.10g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物10(72mg，收率66％)。1H NMR(400MHz,CDCl3)δ7.47(d,J＝8.3Hz,2H),7.33–7.31(m,3H),7.21–7.18(m,4H),5.09–4.97(m,2H),3.03–2.87(m,3H),2.65(dd,J＝12.3,8.1Hz,1H),2.45–2.24(m,5H),1.53–1.48(m,4H),1.43–1.35(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.20,144.99,135.86,132.17,129.77,128.53,128.34,128.29,119.02,110.28,66.23,60.77,54.74,45.67,36.64,26.08,24.38ppm.IR:2934,2227,1731,1607,1454,1152,734,696,562cm-1.HRMS(ESI)for C23H27N2O2 +[(M+H)+]:calculated 363.2067,found 363.2059。
实施例8
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-8(0.11g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物11(65mg，收率57％)。1H NMR(600MHz,CDCl3)δ7.81(d,J＝8.2Hz,2H),7.29–7.28(m,3H),7.22–7.19(m,4H),5.03(d,J＝1.2Hz,2H),3.03–2.97(m,1H),2.95–2.89(m,2H),2.68–2.65(m,1H),2.56(s,3H),2.45–2.22(m,5H),1.53–1.47(m,4H),1.42–1.34(m,2H)ppm.13C NMR(151MHz,CDCl3)δ197.89,174.56,145.09,136.02,135.51,129.20,128.60,128.49,128.24,128.15,66.16,60.92,54.76,45.82,36.69,26.67,26.10,24.43ppm.IR:2933,1732,1680,1606,1356,1266,1151,734,696,597cm-1.HRMS(ESI)for C24H30NO3 +[(M+H)+]:calculated 380.2220,found 380.2212。
实施例9
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-9(0.12g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物12(90mg，收率76％)。1H NMR(400MHz,CDCl3)δ7.36–7.27(m,3H),7.25–7.19(d,J＝7.8Hz,2H),7.13(d,J＝8.6Hz,2H),6.95(d,J＝8.6Hz,2H),5.10–4.98(m,2H),3.04–2.94(m,1H),2.90–2.78(m,2H),2.66(dd,J＝12.3,8.9Hz,1H),2.49–2.34(m,3H),2.32–2.23(m,5H),1.56–1.44(m,4H),1.40–1.34(m,2H)ppm.13C NMR(151MHz,CDCl3)δ174.85,169.54,149.24,136.83,136.11,129.88,128.48,128.21,128.06,121.46,66.09,60.96,54.71,46.04,36.13,26.07,24.43,21.22ppm.IR:2928,1764,1728,1187,1146,908,748,702cm- 1.HRMS(ESI)for C24H30NO4 +[(M+H)+]:calculated 396.2169,found 396.2156.m.p.56.8℃–58.6℃。
实施例10
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-10(0.12g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物13(72mg，收率59％)。1H NMR(600MHz,CDCl3)δ7.90(dd,J＝8.3,2.4Hz,2H),7.35–7.26(m,3H),7.20–7.15(m,4H),5.03(d,J＝2.5Hz,2H),4.37(qd,J＝7.1,2.2Hz,2H),3.02–2.95(m,1H),2.92–2.88(m,2H),2.66(t,J＝10.6Hz,1H),2.49–2.23(m,5H),1.53–1.45(m,4H),1.43–1.31(m,5H)ppm.13C NMR(151MHz,CDCl3)δ174.62,166.68,144.68,136.05,129.78,128.98,128.74,128.50,128.23,128.14,66.15,60.94,54.77,45.88,36.74,26.12,24.45,14.48ppm.IR:2934,1714,1610,1486,1155,1272,1101,1021,751,697cm-1.HRMS(ESI)for C25H32NO4 +[(M+H)+]:calculated 410.2326,found 410.2308。
实施例11
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-11(0.15g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物14(87mg，收率62％)。1H NMR(400MHz,CDCl3)δ7.34–7.21(m,5H),6.98(d,J＝8.6Hz,2H),6.71(d,J＝8.4Hz,2H),5.07(d,J＝12.5Hz,1H),5.00(d,J＝12.4Hz,1H),2.99–2.91(m,1H),2.84–2.58(m,3H),2.48–2.21(m,5H),1.52–1.43(m,4H),1.38–1.34(m,2H),0.97(s,9H),0.17(s,6H)ppm.13C NMR(101MHz,CDCl3)δ175.17,154.21,136.27,131.88,129.91,128.51,128.19,128.06,120.03,66.05,60.97,54.72,46.30,36.24,26.07,25.83,24.45,18.33,-4.29ppm.IR:2930,1735,1609,1509,1252,1150,913,837,779,695cm-1.HRMS(ESI)for C28H42NO3Si+[(M+H)+]:calculated 468.2929,found468.2922。
实施例12
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-12(0.11g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物15(93mg，收率81％)。1H NMR(600MHz,CDCl3)δ7.33–7.26(m,3H),7.21–7.16(m,2H),7.12(d,J＝8.3Hz,2H),7.05(d,J＝8.3Hz,2H),5.06–5.01(m,2H),2.99–2.94(m,1H),2.85–2.77(m,2H),2.66(dd,J＝12.4,9.2Hz,1H),2.44(s,3H),2.43–2.18(m,5H),1.53–1.45(m,4H),1.41–1.34(m,2H)ppm.13C NMR(151MHz,CDCl3)δ174.88,136.22,136.15,136.07,129.47,128.45,128.13,128.04,126.96,66.01,60.97,54.73,46.11,36.30,26.10,24.45,16.16ppm.IR:2932,1732,1495,1150,733,696cm-1.HRMS(ESI)for C23H30NO2S+[(M+H)+]:calculated 384.1992,found 384.1979。
实施例13
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-13(0.14g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物16(0.10g，收率74％)。1H NMR(400MHz,CDCl3)δ7.36–7.23(m,7H),7.18(d,J＝8.1Hz,2H),5.12–4.99(m,2H),4.00–3.28(m,8H),3.03–2.82(m,3H),2.66(dd,J＝12.4,8.6Hz,1H),2.47–2.23(m,5H),1.55–1.44(m,4H),1.43–1.33(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.66,170.50,141.51,136.05,133.33,129.13,128.52,128.18,128.15,127.42,66.99,66.16,60.90,54.73,45.89,36.47,26.07,24.41ppm.IR:2932,1731,1631,1425,1276,1257,1151,1112,1012,749,736,697cm-1.HRMS(ESI)for C27H35N2O4 +[(M+H)+]:calculated 451.2591,found 451.2582。
实施例14
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-14(0.10g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物17(70mg，收率66％)。1H NMR(600MHz,CDCl3)δ7.36–7.28(m,3H),7.20(d,J＝7.0Hz,2H),7.07(t,J＝8.1Hz,2H),6.89(t,J＝9.8Hz,2H),5.04(s,2H),2.98–2.92(m,1H),2.86–2.79(m,2H),2.65(dd,J＝14.0,7.4Hz,1H),2.40–2.22(m,5H),1.54–1.42(m,4H),1.44–1.35(m,2H)ppm.13C NMR(151MHz,CDCl3)δ174.85,161.67(d,JC,F＝244.6Hz),136.13,134.88(d,JC,F＝3.0Hz),130.42(d,JC,F＝7.6Hz),128.52,128.23,128.15,115.24(d,JC,F＝21.1Hz),66.11,60.95,54.77,46.27,36.03,26.12,24.46ppm.IR:2933,1732,1509,1219,1150,749,696cm-1.HRMS(ESI)for C22H27NO2F+[(M+H)+]:calculated 356.2020,found 356.2014。
实施例15
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-15(0.11g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物18(81mg，收率73％)。1H NMR(600MHz,CDCl3)δ7.35–7.27(m,3H),7.21–7.14(m,4H),7.04(d,J＝8.4Hz,1H),5.03(qd,J＝12.3,2.4Hz,2H),3.01–2.91(m,1H),2.85–2.79(m,2H),2.64(dd,J＝12.2,9.0Hz,1H),2.46–2.22(m,5H),1.54–1.45(m,4H),1.42–1.31(m,2H)ppm.13C NMR(151MHz,CDCl3)δ174.73,137.75,136.08,132.21,130.37,128.59,128.53,128.23,128.16,66.14,60.94,54.78,46.10,36.15,26.14,24.47ppm.IR:2933,1732,1492,1150,733,696cm-1.HRMS(ESI)for C22H27NO2Cl+[(M+H)+]:calculated372.1725,found372.1715。
实施例16
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-16(0.13g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物19(81mg，收率64％)。1H NMR(400MHz,CDCl3)δ7.34–7.27(m,3H),7.23–7.18(m,2H),7.13(d,J＝8.7Hz,2H),7.06(d,J＝8.4Hz,2H),5.03(s,2H),3.00–2.93(m,1H),2.89–2.81(m,2H),2.66(dd,J＝12.3,8.7Hz,1H),2.45–2.23(m,5H),1.55–1.45(m,4H),1.43–1.34(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.72,147.84,138.07,136.04,130.28,128.53,128.29,128.20,120.95,66.21,60.94,54.77,46.08,36.04,26.12,24.46ppm.IR:2935,1733,1508,1254,1150,696cm-1.HRMS(ESI)for C23H27F3NO3 +[(M+H)+]:calculated422.1938,found422.1927。
实施例17
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-17(82mg,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物20(47mg，收率43％)。1H NMR(400MHz,CDCl3)δ7.32–7.23(m,6H),7.19–7.13(m,2H),7.09(d,J＝8.1Hz,2H),6.68(dd,J＝17.6,10.9Hz,1H),5.71(d,J＝17.6Hz,1H),5.21(d,J＝10.9Hz,1H),5.04(d,J＝2.6Hz,2H),3.05–2.97(m,1H),2.90–2.79(m,2H),2.73–2.68(m,1H),2.47–2.25(m,5H),1.56–1.46(m,4H),1.43–1.35(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.94,138.85,136.74,136.13,135.86,129.17,128.49,128.19,128.06,126.38,113.36,66.12,60.91,54.70,45.98,36.72,25.98,24.37ppm.IR:2933,1732,1512,1455,1213,1150,991,907,845,827,730,696cm-1.HRMS(ESI)for C24H30NO2 +[(M+H)+]:calculated364.2271,found 364.2263。
实施例18
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-18(89mg,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物21(72mg，收率64％)。1H NMR(400MHz,CDCl3)δ7.34–7.26(m,3H),7.22–7.15(m,2H),7.02(d,J＝8.2Hz,2H),6.93(d,J＝8.2Hz,2H),5.03(d,J＝2.0Hz,2H),3.01–2.94(m,1H),2.86–2.75(m,2H),2.68(dd,J＝12.4,9.3Hz,1H),2.46–2.22(m,5H),1.88–1.84(m,1H),1.56–1.45(m,4H),1.41–1.30(m,2H),0.96–0.88(m,2H),0.69–0.60(m,2H)ppm.13C NMR(101MHz,CDCl3)δ175.08,141.98,136.22,136.13,128.85,128.44,128.13,128.00,125.76,66.02,60.99,54.71,46.14,36.54,26.04,24.43,15.15,9.18,9.17ppm.IR:2932,1732,1518,1455,1149,1018,813,733,696cm-1.HRMS(ESI)for C25H32NO2 +[(M+H)+]:calculated 378.2428,found 378.2416。
实施例19
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-19(0.13g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物22(65mg，收率47％)。1H NMR(400MHz,CDCl3)δ7.72–7.66(m,2H),7.32–7.26(m,3H),7.20–7.15(m,4H),5.03(s,2H),3.04–2.96(m,1H),2.92–2.81(m,2H),2.69–2.63(m,1H),2.42–2.20(m,5H),1.52–1.44(m,4H),1.40–1.36(m,2H),1.34(s,12H)ppm.13C NMR(101MHz,CDCl3)δ174.92,142.62,136.20,135.03,128.46,128.42,128.12,128.00,83.79,66.03,61.00,54.74,45.97,37.07,26.11,25.00,24.98,24.47ppm.IR:2961,2933,1734,1611,1358,1258,1143,1088,1021,859,784,696,658cm-1.HRMS(ESI)for C28H39BNO4 +[(M+H)+]:calculated 464.2967,found 464.2962。
实施例20
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-20(0.10g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物23(95mg，收率77％)。1H NMR(400MHz,CDCl3)δ7.39(d,J＝8.1Hz,2H),7.32–7.26(m,3H),7.23–7.18(m,2H),7.13(d,J＝7.9Hz,2H),5.04(s,2H),3.04–2.97(m,1H),2.91–2.79(m,2H),2.68(dd,J＝12.4,9.3Hz,1H),2.54–2.18(m,5H),1.52–1.44(m,4H),1.40–1.35(m,2H),0.25(s,9H)ppm.13C NMR(101MHz,CDCl3)δ175.09,139.87,138.06,136.21,133.54,128.48,128.38,128.20,128.05,66.11,61.10,54.75,46.02,36.89,26.12,24.48,-0.93ppm.IR:2935,1733,1600,1455,1381,1246,1150,1107,832,751,695cm-1.HRMS(ESI)for C25H36NO2Si+[(M+H)+]:calculated 410.2510,found 410.2500。
实施例21
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-21(93mg,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物24(90mg，收率77％)。1H NMR(400MHz,CDCl3)δ7.79–7.76(m,1H),7.73–7.70(m,2H),7.59(s,1H),7.45–7.38(m,2H),7.27(d,J＝8.3Hz,1H),7.22–7.13(m,3H),7.08(d,J＝7.6Hz,2H),5.01(s,2H),3.15–2.97(m,3H),2.72(dd,J＝12.4,8.9Hz,1H),2.48–2.26(m,5H),1.55–1.44(m,4H),1.42–1.34(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.98,136.80,136.09,133.63,132.33,128.37,128.08,128.02,127.95,127.69,127.46,127.35,126.01,125.44,66.02,61.12,54.76,46.07,37.06,26.12,24.47ppm.IR:2932,1731,1600,1454,1276,1147,815,743,696cm-1.HRMS(ESI)for C26H30NO2 +[(M+H)+]:calculated 388.2271,found388.2252.m.p.52.3℃–53.6℃。
实施例22
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-22(0.11g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物25(69mg，收率56％)。1H NMR(400MHz,CDCl3)δ7.78(t,J＝7.8Hz,1H),7.34–7.27(m,3H),7.25–7.20(m,2H),6.97–6.90(m,2H),5.05(s,2H),3.92(s,3H),3.02–2.94(m,1H),2.93–2.87(m,2H),2.64(dd,J＝12.4,8.3Hz,1H),2.46–2.23(m,5H),1.53–1.47(m,4H),1.43–1.35(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.27,164.93(d,JC,F＝4.0Hz),161.94(d,JC,F＝260.6Hz),147.37(d,JC,F＝9.1Hz),135.91,132.20,128.43(d,JC,F＝25.3Hz),128.25,124.67(d,JC,F＝3.0Hz),117.41(d,JC,F＝23.2Hz),116.61(d,JC,F＝10.1Hz),66.31,60.76,54.76,52.31,45.52,36.28,36.27,26.10,24.42ppm.IR:2934,1729,1622,1437,1295,1260,1150,1087,776,750,696cm-1.HRMS(ESI)for C24H29FNO4 +[(M+H)+]:calculated 414.2075,found 414.2059。
实施例23
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-23(0.14g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物26(0.10g，收率68％)。1H NMR(400MHz,CDCl3)δ7.60(d,J＝8.2Hz,2H),7.36–7.28(m,5H),7.25–7.20(m,2H),5.08–5.01(m,2H),3.74–3.72(m,4H),3.04–2.90(m,7H),2.70–2.63(m,1H),2.42–2.24(m,5H),1.53–1.46(m,4H),1.43–1.36(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.33,145.32,135.84,133.09,129.72,128.58,128.30,128.29,128.02,66.32,66.16,60.82,54.73,46.07,45.67,36.35,26.08,24.38ppm.IR:2936,2857,1730,1455,1349,1162,1112,941,757,741,720,702cm-1.HRMS(ESI)for C26H35N2O5S+[(M+H)+]:calculated487.2261,found 487.2241.m.p.99.8℃–101.7℃。
实施例24
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-24(0.16g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物27(76mg，收率52％)。1H NMR(400MHz,CDCl3)δ7.35–7.23(m,8H),7.20–7.13(m,2H),7.07(d,J＝8.2Hz,2H),6.83(d,J＝8.0Hz,2H),5.07(d,J＝12.4Hz,1H),4.98(d,J＝12.4Hz,1H),4.84(d,J＝3.1Hz,2H),2.99–2.78(m,3H),2.65(dd,J＝12.4,8.7Hz,1H),2.42–2.21(m,5H),1.83(s,3H),1.51–1.43(m,4H),1.40–1.34(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.68,170.52,141.16,139.25,137.63,136.04,130.04,128.84,128.52,128.41,128.24,128.21,128.10,127.38,66.14,60.90,54.72,52.84,45.99,36.18,26.07,24.41,22.77ppm.IR:2932,1732,1656,1510,1387,1151,735,698cm-1.HRMS(ESI)for C31H37N2O3 +[(M+H)+]:calculated485.2799,found 485.2789。
实施例25
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-25(0.16g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物28(82mg，收率52％)。1H NMR(400MHz,CDCl3)δ8.29(d,J＝8.3Hz,1H),8.14(d,J＝8.5Hz,1H),7.90(dd,J＝7.7,1.4Hz,1H),7.75(d,J＝1.8Hz,1H),7.45(t,J＝8.5Hz,1H),7.32(t,J＝6.9Hz,1H),7.23(dd,J＝8.6,1.9Hz,1H),7.19–7.12(m,5H),5.02(s,2H),3.14–2.96(m,3H),2.73(dd,J＝12.4,9.0Hz,1H),2.46–2.21(m,5H),1.75(s,9H),1.57–1.47(m,4H),1.43–1.35(m,2H)ppm.13C NMR(101MHz,CDCl3)δ175.05,151.20,138.84,137.27,136.11,133.94,128.35,128.09,127.95,127.10,125.98,125.79,123.01,119.79,119.68,116.36,116.23,83.88,66.03,61.04,54.78,46.51,36.78,28.51,26.12,24.47ppm.IR:2932,1722,1449,1356,1304,1220,1150,1115,746,696cm-1.HRMS(ESI)forC33H39N2O4 +[(M+H)+]:calculated527.2904,found 527.2896。
实施例26
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-26(0.12g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物29(98mg，收率74％)。1H NMR(400MHz,CDCl3)δ8.08–8.03(m,1H),7.92(d,J＝1.7Hz,1H),7.84–7.79(m,1H),7.68(d,J＝8.2Hz,1H),7.44–7.38(m,2H),7.23–7.21(m,1H),7.19–7.08(m,5H),5.07–4.95(m,2H),3.15–3.07(m,1H),3.05–2.98(m,2H),2.74(dd,J＝12.5,8.7Hz,1H),2.51–2.20(m,5H),1.57–1.46(m,4H),1.42–1.35(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.92,139.85,137.50,135.99,135.82,135.53,135.50,128.37,128.07,127.98,127.93,126.72,124.35,122.89,122.72,121.88,121.69,66.10,60.96,54.74,46.35,36.89,26.06,24.41ppm.IR:2931,1731,1431,1148,1025,763,731,695cm- 1.HRMS(ESI)for C28H30NO2S+[(M+H)+]:calculated 444.1992,found 444.1980。
实施例27
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-27(85mg,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物30(96mg，收率87％)。1H NMR(400MHz,CDCl3)δ8.00(d,J＝5.3Hz,1H),7.37–7.29(m,3H),7.28–7.22(m,2H),6.65(dd,J＝5.3,1.5Hz,1H),6.54(d,J＝1.4Hz,1H),5.06(s,2H),3.90(s,3H),3.02–2.92(m,1H),2.86–2.77(m,2H),2.64(dd,J＝12.3,8.7Hz,1H),2.46–2.23(m,5H),1.52–1.47(m,4H),1.43–1.36(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.43,164.60,151.21,146.81,136.02,128.56,128.25,128.20,117.77,110.92,66.31,60.88,54.77,53.43,45.05,35.83,26.11,24.44ppm.IR:2934,1732,1610,1560,1449,1397,1314,1152,1044,990,735,696cm-1.HRMS(ESI)for C22H29N2O3 +[(M+H)+]:calculated369.2173,found 369.2164。
实施例29
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-29(0.16g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物32(0.10g，收率70％)。1H NMR(400MHz,CDCl3)δ7.99(d,J＝8.4Hz,1H),7.56(d,J＝3.7Hz,1H),7.31(d,J＝1.7Hz,1H),7.26–7.21(m,3H),7.18–7.13(m,2H),7.09(dd,J＝8.6,1.9Hz,1H),6.47(d,J＝3.7Hz,1H),5.02(s,2H),3.09–3.00(m,1H),3.00–2.89(m,2H),2.70(dd,J＝12.4,9.1Hz,1H),2.50–2.21(m,5H),1.66(s,9H),1.54–1.46(m,4H),1.43–1.34(m,2H)ppm.13C NMR(101MHz,CDCl3)δ175.09,149.86,136.20,133.48,130.82,128.34,128.05,127.91,126.06,125.34,121.04,115.05,107.29,83.59,65.92,61.06,54.72,46.57,36.85,28.28,26.08,24.45ppm.IR:2933,1728,1469,1371,1348,1255,1158,1130,1081,1022,766,725,696cm-1.HRMS(ESI)for C29H37N2O4 +[(M+H)+]:calculated477.2748,found 477.2740。
实施例30
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-30(96mg,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物33(75mg，收率63％)。1H NMR(400MHz,CDCl3)δ8.96(s,1H),7.94(d,J＝1.7Hz,1H),7.79(d,J＝8.2Hz,1H),7.27–7.19(m,4H),7.18–7.13(m,2H),5.04(s,2H),3.12–2.99(m,3H),2.71(d,J＝14.5Hz,1H),2.45–2.28(m,5H),1.53–1.48(m,4H),1.40–1.35(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.74,154.18,153.72,137.83,136.06,131.76,128.40,128.10,128.01,126.95,123.74,121.68,66.10,60.90,54.76,46.36,36.69,26.10,24.44ppm.IR:2932,1730,1442,1148,845,734,696cm-1.HRMS(ESI)for C23H27N2O2S+[(M+H)+]:calculated395.1788,found 395.1777。
实施例31
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-31(0.11g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物34(55mg，收率48％)。1H NMR(400MHz,CDCl3)δ7.35–7.21(m,5H),6.69–6.61(m,2H),6.57(dd,J＝7.9,1.7Hz,1H),5.90(s,2H),5.06(d,J＝1.6Hz,2H),2.97–2.87(m,1H),2.81–2.72(m,2H),2.65(dd,J＝12.4,9.3Hz,1H),2.41–2.23(m,5H),1.56–1.44(m,4H),1.43–1.34(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.94,147.63,146.10,136.23,132.98,128.47,128.14,128.05,121.90,109.39,108.23,100.89,66.02,60.91,54.75,46.40,36.61,26.11,24.47ppm.IR:2932,1731,1502,1488,1442,1244,1150,1037,927,807,734,696cm-1.HRMS(ESI)for C23H28NO4 +[(M+H)+]:calculated 382.2013,found382.1997。
实施例32
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-32(94mg,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物35(77mg，收率66％)。1H NMR(400MHz,CDCl3)δ8.86(dd,J＝4.3,1.7Hz,1H),8.02–7.98(m,2H),7.54–7.50(m,2H),7.35(dd,J＝8.3,4.2Hz,1H),7.24–7.15(m,3H),7.10(d,J＝8.2Hz,2H),5.01(d,J＝1.8Hz,2H),3.16–3.09(m,1H),3.08–2.99(m,2H),2.73(dd,J＝12.4,8.5Hz,1H),2.47–2.23(m,5H),1.57–1.47(m,4H),1.43–1.36(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.72,149.97,147.34,137.71,135.93,135.82,131.11,129.49,128.39,128.30,128.09,128.05,127.14,121.21,66.12,61.00,54.74,45.89,36.75,26.04,24.39ppm.IR:2919,1731,1499,1455,1151,836,733,696cm-1.HRMS(ESI)forC25H29N2O2 +[(M+H)+]:calculated 389.2224,found 389.2214。
实施例34
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-34(89mg,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物37(48mg，收率42％)。1H NMR(400MHz,CDCl3)δ7.58(d,J＝2.2Hz,1H),7.37–7.34(m,2H),7.25–7.23(m,3H),7.12(dd,J＝7.2,2.4Hz,2H),7.06(dd,J＝8.3,1.8Hz,1H),6.67(d,J＝2.1Hz,1H),5.02(d,J＝2.4Hz,2H),3.08–2.99(m,1H),2.98–2.90(d,J＝6.7Hz,2H),2.71(dd,J＝12.4,9.1Hz,1H),2.48–2.40(m,3H),2.33–2.24(m,2H),1.56–1.46(m,4H),1.42–1.35(m,2H)ppm.13C NMR(101MHz,CDCl3)δ175.08,153.95,145.20,136.16,133.63,128.42,128.09,128.02,127.64,125.39,121.28,111.22,106.60,66.02,61.04,54.73,46.65,36.90,26.05,24.43ppm.IR:2932,1731,1631,1467,1150,1028,733,696cm-1.HRMS(ESI)for C24H28NO3 +[(M+H)+]:calculated 378.2064,found 378.2054。
实施例35
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2b(38mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物38(91mg，收率80％)。1H NMR(400MHz,CDCl3)δ7.58(d,J＝8.4Hz,2H),7.49(d,J＝8.2Hz,2H),7.48–7.39(m,2H),7.35–7.30(m,1H),7.27–7.24(m,2H),2.87–2.77(m,3H),2.67–2.59(m,1H),2.43–2.35(m,5H),1.57–1.49(m,4H),1.44–1.34(m,2H),1.34(s,9H)ppm.13C NMR(151MHz,CDCl3)δ174.46,141.21,139.14,138.84,129.55,128.84,127.16,127.10,127.01,80.19,61.29,54.72,46.69,36.60,28.13,26.23,24.56ppm.IR:2932,1717,1486,1148,751,699cm-1.HRMS(ESI)for C25H34NO2 +[(M+H)+]:calculated 380.2584,found 380.2571.m.p.50.8℃–52.3℃。
实施例36
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酸酯2c(34mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物39(44mg，收率40％)。1H NMR(600MHz,CDCl3)δ7.57(d,J＝7.0Hz,2H),7.49(d,J＝8.3Hz,2H),7.43–7.40(m,2H),7.32(t,J＝7.4Hz,1H),7.24–7.23(m,2H),5.83–5.76(m,1H),5.21(dq,J＝17.2,1.6Hz,1H),5.14(dq,J＝10.5,1.4Hz,1H),4.52(dd,J＝5.6,1.6Hz,2H),3.03–2.98(m,1H),2.94–2.86(m,2H),2.70–2.66(m,1H),2.44–2.32(m,5H),1.53–1.50(m,4H),1.43–1.37(m,2H)ppm.13C NMR(151MHz,CDCl3)δ174.83,141.11,139.33,138.46,132.38,129.42,128.84,127.21,127.18,127.10,117.90,65.01,60.97,54.76,46.08,36.47,26.14,24.49ppm.IR:2932,1732,1486,1151,762,696cm-1.HRMS(ESI)for C24H30NO2 +[(M+H)+]:calculated 364.2271,found 364.2260。
实施例37
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酰胺2d(44mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(3.0mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物40(56mg，收率47％)。1H NMR(400MHz,CDCl3)δ11.48(s,1H),7.58(dt,J＝8.2,1.6Hz,4H),7.50–7.44(m,2H),7.42(t,J＝7.7Hz,2H),7.33–7.28(m,5H),7.08–7.04(m,1H),3.46(dd,J＝14.1,4.4Hz,1H),2.91–2.83(m,1H),2.72–2.50(m,4H),2.42–2.17(m,3H),1.71–1.56(m,4H),1.55–1.43(m,2H)ppm.13C NMR(101MHz,CDCl3)δ172.34,140.97,139.23,139.17,139.09,129.61,129.05,128.83,127.18,127.02,123.50,119.55,59.64,53.96,42.06,34.34,26.37,24.22ppm.IR:2932,1672,1596,1548,1485,1441,1305,753,691cm-1.HRMS(ESI)for C27H31N2O+[(M+H)+]:calculated 399.2431,found399.2418.m.p.87.1℃–88.7℃。
实施例38
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酰胺2e(48mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(3.0mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物41(77mg，收率62％)。1H NMR(400MHz,CDCl3)δ8.75(t,J＝5.4Hz,1H),7.59–7.57(m,2H),7.50(d,J＝8.1Hz,2H),7.42(t,J＝7.6Hz,2H),7.34–7.22(m,8H),4.47–4.37(m,2H),3.37–3.29(m,1H),2.76–2.67(m,2H),2.56–2.37(m,3H),2.31(dd,J＝12.7,3.4Hz,1H),2.22–2.04(m,2H),1.43–1.26(m,6H)ppm.13C NMR(101MHz,CDCl3)δ174.11,141.04,139.38,139.02,138.87,129.60,128.83,128.62,127.80,127.26,127.17,127.12,127.03,60.16,54.20,43.53,42.94,35.18,25.97,24.20ppm.IR:3312,2930,1646,1538,1244,759,713cm-1.HRMS(ESI)for C28H33N2O+[(M+H)+]:calculated 413.2587,found413.2572.m.p.91.6℃–92.4℃。
实施例39
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酰胺2f(30mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(3.0mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物42(73mg，收率69％)。1H NMR(400MHz,CDCl3)δ7.62–7.57(m,2H),7.49(d,J＝8.3Hz,2H),7.42(t,J＝7.6Hz,2H),7.32(t,J＝7.3Hz,1H),7.23(d,J＝8.3Hz,2H),3.24–3.17(m,1H),2.96–2.82(m,5H),2.78–2.67(m,4H),2.47–2.27(m,5H),1.59–1.52(m,4H),1.43–1.37(m,2H)ppm.13C NMR(151MHz,CDCl3)δ175.00,140.98,139.34,139.06,129.43,128.83,127.20,126.99,126.97,61.90,55.11,42.07,37.45,37.23,35.81,26.14,24.39ppm.IR:2921,1633,1483,1394,761,693cm-1.HRMS(ESI)for C23H31N2O+[(M+H)+]:calculated351.2431,found 351.2421.m.p.109.8℃–110.7℃。
实施例40
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酰胺2g(75mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(3.0mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物43(113mg，收率75％)。1H NMR(400MHz,CDCl3)δ7.59(d,J＝9.1Hz,2H),7.50–7.40(m,4H),7.36–7.32(m,1H),7.31–7.07(m,10H),6.91–6.82(m,2H),4.93(d,J＝14.9Hz,1H),4.54(d,J＝17.1Hz,1H),4.19(d,J＝14.9Hz,1H),4.11(d,J＝17.1Hz,1H),3.21–3.14(m,1H),3.01(dd,J＝13.1,9.1Hz,1H),2.82–2.76(m,2H),2.44–2.32(m,5H),1.56–1.46(m,4H),1.43–1.35(m,2H)ppm.13C NMR(101MHz,CDCl3)δ175.90,141.11,139.40,139.08,137.41,137.14,129.81,128.90,128.84,128.50,128.28,127.39,127.21,127.19,127.15,127.05,126.58,62.96,55.57,49.81,48.71,43.00,37.21,26.19,24.43ppm.IR:2932,1637,1442,1218,728,695cm-1.HRMS(ESI)for C35H39N2O+[(M+H)+]:calculated 503.3057,found 503.3044。
实施例41
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酰胺2h(67mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(3.0mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物44(117mg，收率82％)。1H NMR(600MHz,CDCl3)δ7.64–7.60(m,2H),7.54(d,J＝8.2Hz,2H),7.47–7.43(m,2H),7.36–7.33(m,1H),7.27–7.17(m,7H),7.12(dd,J＝7.9,5.4Hz,3H),3.02–2.96(m,2H),2.90–2.86(m,1H),2.75–2.70(m,1H),2.37–2.17(m,5H),1.59–1.52(m,4H),1.47–1.37(m,2H)ppm.13C NMR(151MHz,CDCl3)δ175.34,143.27,142.78,141.14,139.42,139.18,129.99,129.20,129.15,128.92,128.87,127.55,127.30,127.12,127.10,126.79,126.10,63.09,55.41,43.94,37.54,26.30,24.48ppm.IR:2931,1663,1489,1259,691cm-1.HRMS(ESI)for C33H35N2O+[(M+H)+]:calculated 475.2744,found475.2737.m.p.110.5℃–111.8℃。
实施例42
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酰胺2i(48mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(3.0mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物45(77mg，收率62％)。1H NMR(400MHz,CDCl3)δ7.63–7.60(m,2H),7.50–7.43(m,4H),7.35(td,J＝7.1,1.3Hz,1H),7.25–7.20(m,3H),7.07(d,J＝8.0Hz,2H),3.15(s,3H),2.91–2.73(m,3H),2.65(dd,J＝12.3,3.5Hz,1H),2.26–2.03(m,5H),1.54–1.46(m,4H),1.41–1.35(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.80,143.84,141.18,139.38,139.17,129.70,129.16,128.90,127.85,127.53,127.24,127.06,126.98,62.42,55.28,43.24,37.52,37.41,26.16,24.48ppm.IR:2932,1649,1594,1495,1118,765,696cm-1.HRMS(ESI)for C28H33N2O+[(M+H)+]:calculated 413.2587,found 413.2578。
实施例43
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酰胺2j(48mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(3.0mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物46(77mg，收率65％)。1H NMR(400MHz,CDCl3)δ7.56(dd,J＝7.5,1.7Hz,2H),7.50(d,J＝8.1Hz,2H),7.43(dd,J＝8.4,6.9Hz,2H),7.35–7.31(m,1H),7.23(d,J＝8.1Hz,2H),3.69–3.55(m,2H),3.47–3.27(m,4H),3.21–3.07(m,2H),2.94–2.76(m,4H),2.49–2.32(m,5H),1.61–1.49(m,4H),1.45–1.37(m,2H)ppm.13C NMR(101MHz,CDCl3)δ173.58,140.92,139.42,139.03,129.53,128.88,127.29,127.17,127.04,66.91,66.52,62.23,55.16,46.18,42.28,41.54,37.63,26.17,24.37ppm.IR:2916,1625,1456,1441,1102,798,697cm-1.HRMS(ESI)for C25H33N2O2 +[(M+H)+]:calculated 393.2537,found 393.2519.m.p.122.6℃–123.7℃。
实施例44
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1a(77mg,0.45mmol,1.5当量)，丙烯酰胺2k(46mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(3.0mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物47(52mg，收率43％)。1H NMR(600MHz,CDCl3)δ7.56–7.54(m,2H),7.47(d,J＝8.2Hz,2H),7.42(t,J＝7.7Hz,2H),7.33(d,J＝7.4Hz,1H),7.25(d,J＝8.1Hz,2H),3.57–3.53(m,1H),3.37–3.33(m,1H),3.24–3.07(m,3H),2.95(dd,J＝13.1,9.9Hz,1H),2.84(dd,J＝13.1,4.7Hz,1H),2.70(dd,J＝12.6,7.7Hz,1H),2.46–2.32(m,5H),1.65–1.50(m,7H),1.45–1.36(m,4H),1.31–1.25(m,2H),1.16–1.06(m,1H)ppm.13C NMR(151MHz,CDCl3)δ174.51,141.26,139.66,139.14,129.72,128.84,127.15,127.07,127.05,62.35,55.36,47.64,45.99,42.89,37.42,29.07,27.93,26.72,26.50,26.27,24.49ppm.IR:2923,2851,1628,1483,1443,1247,1147,1104,997,870,760,740,694cm-1.HRMS(ESI)for C27H37N2O+[(M+H)+]:calculated405.2900,found 405.2896.m.p.93.1℃–95.2℃。
实施例46
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1b(97mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物49(84mg，收率61％)。1H NMR(400MHz,CDCl3)δ7.57(dd,J＝7.1,1.5Hz,2H),7.48–7.41(m,4H),7.32(d,J＝9.4Hz,1H),7.28–7.23(m,3H),7.20(d,J＝6.2Hz,2H),7.18–7.13(m,2H),5.05(d,J＝12.3Hz,1H),4.99(d,J＝12.4Hz,1H),3.00–2.93(m,1H),2.89–2.77(m,3H),2.54–2.29(m,5H),1.40–1.33(m,4H),1.31–1.21(m,4H),0.88(t,J＝7.2Hz,6H)ppm.13C NMR(101MHz,CDCl3)δ175.12,141.11,139.28,138.61,136.10,129.37,128.86,128.49,128.30,128.09,127.22,127.11,66.17,57.04,54.25,47.40,36.61,29.44,20.72,14.25ppm.IR:2955,2930,1732,1487,1454,1378,1151,756,732,695cm-1.HRMS(ESI)forC31H40NO2 +[(M+H)+]:calculated 458.3054,found 458.3040。
实施例47
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1c(0.13g,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物50(87mg，收率54％)。1H NMR(600MHz,CDCl3)δ7.56(d,J＝9.6Hz,2H),7.46–7.41(m,4H),7.34–7.29(m,1H),7.27–7.19(m,8H),7.16(d,J＝8.3Hz,4H),5.04(s,2H),3.67(d,J＝13.6Hz,1H),3.58(s,3H),3.42(d,J＝13.6Hz,1H),3.05–2.99(m,1H),2.90(dd,J＝12.7,9.4Hz,1H),2.86–2.82(m,2H),2.54(dd,J＝12.7,5.4Hz,1H),2.45(dt,J＝12.9,7.3Hz,1H),2.36(dt,J＝12.9,6.4Hz,1H),2.28(dt,J＝16.2,7.3Hz,1H),2.21(dt,J＝16.2,7.5Hz,1H),1.75–1.70(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.75,174.14,140.99,139.32,139.16,138.18,135.93,129.31,129.02,128.83,128.50,128.40,128.23,128.14,127.22,127.20,127.05,127.01,66.27,58.89,56.57,53.05,51.49,47.16,36.46,31.54,22.28ppm.IR:3028,2949,2808,1731,1487,1452,1153,732,695cm-1.HRMS(ESI)forC35H38NO4 +[(M+H)+]:calculated536.2795,found 536.2773。
实施例48
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1d(0.14g,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物51(0.11g，收率66％)。1H NMR(400MHz,CDCl3)δ7.69–7.64(m,2H),7.60–7.52(m,4H),7.46–7.41(m,1H),7.40–7.34(m,3H),7.33–7.28(m,4H),5.16(s,2H),3.52(d,J＝6.5Hz,2H),3.19–3.12(m,1H),3.07–2.83(m,5H),2.56(dd,J＝12.4,5.6Hz,1H),2.13–2.07(m,1H),2.00(t,J＝12.8Hz,1H),1.77–1.72(m,2H),1.58–1.47(m,1H),1.32–1.18(m,2H),1.00(s,9H),0.15(s,6H)ppm.13C NMR(101MHz,CDCl3)δ174.99,141.07,139.33,138.34,136.17,129.41,128.85,128.50,128.24,128.08,127.23,127.21,127.10,68.29,66.13,60.68,54.22,53.46,46.24,38.70,36.58,29.18,29.04,26.11,18.52,-5.20ppm.IR:2926,2854,1734,1487,1454,1463,1385,1250,1153,1100,1071,834,774,695cm-1.HRMS(ESI)forC35H48NO3Si+[(M+H)+]:calculated 558.3398,found 558.3388。
实施例49
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1e(0.10g,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物52(0.10g，收率71％)。1H NMR(400MHz,CDCl3)δ7.60–7.55(m,2H),7.50–7.38(m,4H),7.36–7.31(m,1H),7.30–7.25(m,3H),7.22–7.16(m,4H),5.06(s,2H),3.66(s,3H),3.06–2.98(m,1H),2.95–2.83(m,3H),2.81–2.70(m,2H),2.42(dd,J＝12.4,5.6Hz,1H),2.27–2.18(m,1H),2.10–2.02(m,1H),1.98–1.92(m,1H),1.85–1.78(m,2H),1.74–1.60(m,2H)ppm.13C NMR(101MHz,CDCl3)δ175.70,174.78,141.00,139.36,138.18,136.08,129.36,128.83,128.51,128.22,128.12,127.23,127.20,127.07,66.15,60.42,53.57,52.76,51.69,46.19,41.10,36.42,28.42,28.33ppm.IR:2948,2920,1728,1646,1486,1439,1147,1072,768,751,695cm-1.HRMS(ESI)for C30H34NO4 +[(M+H)+]:calculated 472.2482,found472.2462.m.p.86.3℃–87.9℃。
实施例50
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1f(99mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物53(89mg，收率64％)。1H NMR(600MHz,CDCl3)δ7.57(dd,J＝8.3,1.3Hz,2H),7.48(d,J＝8.1Hz,2H),7.42(t,J＝7.7Hz,2H),7.34–7.31(m,1H),7.22(d,J＝8.2Hz,2H),7.23–7.16(m,1H),7.13–7.07(m,7H),6.97(d,J＝7.0Hz,1H),5.07–5.00(m,2H),3.71(d,J＝14.7Hz,1H),3.59(d,J＝14.7Hz,1H),3.17–3.12(m,1H),2.98(dd,J＝13.7,9.0Hz,1H),2.94–2.90(m,2H),2.83–2.77(m,3H),2.69–2.61(m,2H)ppm.13C NMR(151MHz,CDCl3)δ174.75,140.98,139.37,138.16,135.98,134.92,134.53,129.39,128.84,128.71,128.39,128.10,128.00,127.23,127.07,126.64,126.13,125.64,66.18,60.15,56.21,51.07,46.37,36.40,29.29ppm.IR:2923,1733,1495,1150,764,739,728,690cm-1.HRMS(ESI)forC32H32NO2 +[(M+H)+]:calculated 462.2428,found 462.2412.m.p.110.5℃–111.℃℃。
实施例51
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1g(0.12g,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物54(60mg，收率40％)。1H NMR(400MHz,CDCl3)δ7.56(d,J＝9.1Hz,2H),7.48–7.41(m,4H),7.37–7.30(m,1H),7.24–7.12(m,9H),7.09–7.02(m,2H),6.93(dd,J＝16.8,7.5Hz,6H),4.93–4.86(m,2H),4.15(dd,J＝14.7,8.9Hz,1H),3.89(dd,J＝14.7,5.3Hz,1H),3.28–3.16(m,1H),2.99(dd,J＝13.7,8.8Hz,1H),2.90(dd,J＝13.7,6.5Hz,1H)ppm.13C NMR(101MHz,CDCl3)δ174.46,147.95,140.98,139.61,137.66,135.68,129.46,129.42,128.90,128.53,128.37,128.23,127.31,127.12,121.91,121.46,66.61,54.22,46.79,36.25ppm.IR:2920,1726,1588,1496,1348,1156,760,744,690cm-1.HRMS(ESI)forC35H32NO2 +[(M+H)+]:calculated 498.2428,found 498.2406.m.p.85.7℃–86.5℃。
实施例52
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1h(0.10g,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物55(0.11g，收率79％)。1H NMR(400MHz,CDCl3)δ7.56(d,J＝9.3Hz,2H),7.43(dd,J＝16.6,9.3Hz,4H),7.35–7.29(m,1H),7.27–7.13(m,12H),5.04(s,2H),3.66(d,J＝13.8Hz,1H),3.48(d,J＝13.8Hz,1H),3.06–2.99(m,1H),2.92–2.82(m,3H),2.59–2.39(m,3H),0.97(t,J＝7.1Hz,3H)ppm.13C NMR(101MHz,CDCl3)δ174.86,141.05,139.69,139.27,138.43,136.06,129.34,128.89,128.84,128.49,128.32,128.21,128.10,127.21,127.19,127.07,126.90,66.19,58.45,55.95,47.62,47.27,36.42,11.70ppm.IR:2918,1731,1487,1453,1151,1072,731,695cm-1.HRMS(ESI)for C32H34NO2 +[(M+H)+]:calculated 464.2584,found 464.2576。
实施例53
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1i(71mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物56(50mg，收率42％)。1H NMR(600MHz,CDCl3)δ7.56(d,J＝7.6Hz,2H),7.47(d,J＝8.1Hz,2H),7.42(t,J＝7.7Hz,2H),7.32(t,J＝7.6Hz,1H),7.25(d,J＝6.8Hz,3H),7.21(d,J＝8.1Hz,2H),7.17(d,J＝7.1Hz,2H),5.05(d,J＝2.5Hz,2H),3.04–2.95(m,1H),2.95–2.88(m,3H),2.56–2.53(m,3H),2.46–2.43(m,2H),1.73(t,J＝6.5Hz,4H)ppm.13C NMR(151MHz,CDCl3)δ174.94,141.05,139.33,138.30,136.12,129.41,128.84,128.46,128.15,128.06,127.22,127.20,127.09,66.17,58.26,54.29,47.86,36.63,23.71ppm.IR:2956,1732,1486,1151,754,732,695cm-1.HRMS(ESI)for C27H30NO2 +[(M+H)+]:calculated400.2271,found400.2264.m.p.42.5℃–44.0℃。
实施例54
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1j(78mg,0.45mmol,1.5当量)，丙烯酸酯2m(26mg,0.30mmol,1.0当量)，芳基卤代物3-13(0.14g,0.45mmol,1.5当量)无水NMP(1.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物57(70mg，收率62％)。1H NMR(400MHz,CDCl3)δ7.33(d,J＝8.2Hz,2H),7.21(d,J＝8.1Hz,2H),3.79–3.47(m,15H),2.97–2.82(m,3H),2.66(d,J＝12.0Hz,1H),2.51–2.36(m,5H)ppm.13C NMR(101MHz,CDCl3)δ174.94,170.47,141.28,133.45,129.06,127.47,67.08,66.97,60.36,53.71,51.70,45.42,36.21ppm.IR:2855,1732,1625,1430,1277,1259,1112,1010,916,868,841,726,646cm-1.HRMS(ESI)for C20H29N2O5 +[(M+H)+]:calculated 377.2071,found 377.2069。
实施例55
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1j(78mg,0.45mmol,1.5当量)，丙烯酸酯2a(49mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(3.0mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物58(77mg，收率62％)。1H NMR(600MHz,CDCl3)δ7.56(d,J＝7.7Hz,2H),7.47(d,J＝6.8Hz,2H),7.42(t,J＝7.3Hz,2H),7.32(t,J＝7.5Hz,1H),7.26(d,J＝5.8Hz,3H),7.20(d,J＝7.5Hz,4H),5.06(s,2H),3.60(s,4H),3.05–3.00(m,1H),2.96–2.92(m,1H),2.86(dd,J＝13.6,6.0Hz,1H),2.73(t,J＝10.9Hz,1H),2.55–2.40(m,3H),2.39–2.29(m,2H)ppm.13C NMR(151MHz,CDCl3)δ174.59,140.94,139.41,138.01,136.02,129.33,128.84,128.50,128.29,128.17,127.25,127.22,127.05,67.01,66.18,60.65,53.76,45.79,36.34ppm.IR:2955,2853,2809,1731,1487,1152,1115,753,731,695cm-1.HRMS(ESI)forC27H30NO3 +[(M+H)+]:calculated 416.2220,found 416.2208.m.p.51.3℃–53.6℃。
实施例57
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(1.2mg,1.5μmol,0.0050当量)，金属催化剂NiBr2·glyme(9.3mg,30μmol,0.10当量)，配体6,6'-di(Me)bpy(5.6mg,30μmol,0.10当量)，α-氨甲基硅1l(0.14g,0.45mmol,1.5当量)，丙烯酰胺2e(48mg,0.30mmol,1.0当量)，芳基卤代物3-6(0.13g,0.45mmol,1.5当量)无水NMP(3.0mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物60(0.13g，收率79％)。1H NMR(400MHz,CDCl3)δ8.04(d,J＝7.1Hz,2H),7.61–7.52(m,3H),7.48(d,J＝8.2Hz,2H),7.43(t,J＝7.7Hz,4H),7.36–7.30(m,1H),7.28–7.17(m,7H),5.06(s,2H),4.15(d,J＝6.2Hz,2H),3.08–2.81(m,5H),2.76(dd,J＝12.3,9.3Hz,1H),2.45(dd,J＝12.4,5.6Hz,1H),2.07–1.99(m,1H),1.93(t,J＝11.5Hz,1H),1.79–1.68(m,3H),1.39–1.23(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.90,166.68,141.02,139.36,138.25,136.12,133.00,130.50,129.66,129.38,128.85,128.51,128.47,128.27,128.13,127.24,127.21,127.08,69.35,66.15,60.60,53.95,53.07,46.23,36.54,35.56,29.22,29.06ppm.IR:2939,1716,1487,1450,1269,1152,1107,711,695cm-1.HRMS(ESI)forC36H38NO4 +[(M+H)+]:calculated 548.2795,found 548.2787。
实施例58
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(0.40mg,0.050μmol,0.0050当量)，金属催化剂NiBr2·glyme(3.1mg,10μmol,0.10当量)，配体6,6'-di(Me)bpy(1.9mg,10μmol,0.10当量)，α-氨甲基硅1m(0.41mg,0.15mmol,1.5当量)，丙烯酸酯2m(8.6mg,0.10mmol,1.0当量)，芳基卤代物3-1(31mg,0.15mmol,1.5当量)无水NMP(0.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物61(26mg，收率71％)。1H NMR(400MHz,CDCl3)δ7.29–7.24(m,4H),7.22–7.15(m,4H),7.14–7.10(m,1H),5.05(s,2H),3.62(s,3H),3.04–2.97(m,1H),2.96–2.83(m,3H),2.82–2.70(m,2H),2.53–2.43(m,2H),2.37(t,J＝13.2Hz,1H),1.97–1.88(m,2H),1.75–1.69(m,2H)ppm.13C NMR(101MHz,CDCl3)δ175.57,145.82,139.27,139.06,128.93,128.51,127.66,127.42,126.48,121.17,120.92,84.76,70.80,60.32,51.64,50.69,50.00,46.14,36.93,36.76,36.72ppm.IR:2917,2849,1733,1455,1374,1210,1162,1048,1019,755,721,699cm-1.HRMS(ESI)for C23H28NO3 +[(M+H)+]:calculated 366.2064,found 366.2056。
实施例59
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(0.40mg,0.050μmol,0.0050当量)，金属催化剂NiBr2·glyme(3.1mg,10μmol,0.10当量)，配体6,6'-di(Me)bpy(1.9mg,10μmol,0.10当量)，α-氨甲基硅1m(0.41mg,0.15mmol,1.5当量)，丙烯酸酯2m(8.6mg,0.10mmol,1.0当量)，芳基卤代物3-27(28mg,0.15mmol,1.5当量)无水NMP(0.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物62(22mg，收率55％)。1H NMR(400MHz,CDCl3)δ8.05(d,J＝5.3Hz,1H),7.28–7.24(m,2H),7.22–7.18(m,1H),7.15–7.11(m,1H),6.71(dd,J＝5.3,1.5Hz,1H),6.58(s,1H),5.05(s,2H),3.92(s,3H),3.65(s,3H),3.02–2.94(m,1H),2.91–2.81(m,3H),2.78–2.72(m,2H),2.52–2.34(m,3H),1.95–1.87(m,2H),1.76–1.70(m,2H)ppm.13C NMR(101MHz,CDCl3)δ174.97,164.65,151.30,146.85,145.77,139.08,127.70,127.44,121.20,120.92,117.75,110.91,84.73,70.83,60.25,53.47,51.84,50.52,50.26,45.06,36.78,35.84ppm.IR:2945,2815,1734,1610,1560,1481,1449,1397,1313,1157,1047,756,720cm-1.HRMS(ESI)for C23H29N2O4 +[(M+H)+]:calculated 397.2122,found 397.2116。
实施例60
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(0.40mg,0.050μmol,0.0050当量)，金属催化剂NiBr2·glyme(3.1mg,10μmol,0.10当量)，配体6,6'-di(Me)bpy(1.9mg,10μmol,0.10当量)，α-氨甲基硅1m(0.41mg,0.15mmol,1.5当量)，丙烯酰胺2e(16.2mg,0.10mmol,1.0当量)，芳基卤代物3-1(31mg,0.15mmol,1.5当量)无水NMP(0.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物63(19mg，收率43％)。1H NMR(400MHz,CDCl3)δ8.65(t,J＝5.2Hz,1H),7.37–7.24(m,9H),7.21–7.14(m,4H),6.89–6.85(m,1H),4.98(s,2H),4.49–4.39(m,2H),3.33(dd,J＝13.4,4.9Hz,1H),2.87–2.82(m,1H),2.69–2.57(m,3H),2.52–2.40(m,2H),2.23–1.99(m,2H),1.68–1.56(m,4H)ppm.13C NMR(101MHz,CDCl3)δ174.05,145.27,140.10,138.96,138.86,129.16,128.77,128.51,128.04,127.77,127.44,127.36,126.26,121.21,120.74,84.33,70.79,59.57,51.44,48.15,43.78,43.33,36.58,36.36,35.64ppm.IR:3261,2913,1638,1571,1496,1486,1452,1428,1382,1050,1027,759,730,720,696cm- 1.HRMS(ESI)for C29H33N2O2 +[(M+H)+]:calculated 441.2537,found 441.2526.m.p.154.8℃–156.3℃。
实施例61
氮气氛围的手套箱中，在10mL透明玻璃反应管中加入磁力搅拌子，光催化剂4CzIPN(0.40mg,0.050μmol,0.0050当量)，金属催化剂NiBr2·glyme(3.1mg,10μmol,0.10当量)，配体6,6'-di(Me)bpy(1.9mg,10μmol,0.10当量)，α-氨甲基硅1n(0.41mg,0.15mmol,1.5当量)，丙烯酸酯2m(8.6mg,0.10mmol,1.0当量)，芳基卤代物3-1(31mg,0.15mmol,1.5当量)无水NMP(0.5mL)，塞子封闭管口，置于蓝光照射下室温反应24小时，之后用饱和碳酸氢钠溶液淬灭反应，乙酸乙酯萃取(20mL x 3次)，有机相合并，无水硫酸钠干燥，过滤，旋干，柱层析得到产物64(32mg，收率88％)。1H NMR(400MHz,CDCl3)δ7.30–7.24(m,2H),7.22–7.11(m,7H),3.62(s,3H),3.03–2.83(m,6H),2.80–2.69(m,2H),2.48(dd,J＝12.4,5.6Hz,1H),2.26–2.12(m,2H),1.97(t,J＝7.4Hz,2H),1.94–1.84(m,2H),1.52–1.46(m,2H)ppm.13C NMR(101MHz,CDCl3)δ175.64,151.46,143.22,139.31,128.94,128.79,128.51,126.76,126.47,124.66,122.63,60.49,51.63,51.52,51.15,46.41,46.09,36.99,36.97,36.93,34.98,29.98ppm.IR:2923,1734,1455,1436,1376,1162,755,699cm-1.HRMS(ESI)forC24H30NO2 +[(M+H)+]:calculated 364.2271,found 364.2262。
实施例62
该实施例其他条件同实施例6，唯一不同的是，将该实施例中的配体替换为L2-L11，其它条件相同，得到产物9的收率分别为：L2(69％)，L3(76％)，L4(70％)，L5(76％)，L6(56％)，L7(73％)，L8(77％)，L9(30％)，L10(33％)，L11(45％)。
本发明具体实施例1-62中采用的α-氨甲基硅的结构选自如下(与具体实施例中采用的编号对应)：
本发明具体实施例1-62中烯烃2a、2b……2m的结构选自如下：
本发明具体实施例1-62中芳基(或杂芳基)卤代物3-1、3-2……3-34的结构如下：
本发明具体实施例1-62中光催化剂的结构如下：
本发明具体实施例1-62中采用配体的结构式如下：
本发明具体实施例1-61中产物4-64的结构式如下：
对比例1
该对比例其他条件同实施例6，唯一不同的是，将该实施例中的氨甲基硅替换为三级胺、氨基酸或者氨甲基三氟硼酸盐，然而，都得不到目标产物。
对比例2
该对比例其他条件同实施例6，唯一不同的是，将该实施例中的氮原子邻位有取代基的氮配体替换为其它氮原子邻位无取代基的氮配体，如L12-L17，然而，得到最终产物的收率均小于5％。
实施例62为在实施例6的基础上，仅更换配体种类后进行合成的实验结果。通过上述实施例也可以看出相对于其他配体结构，采用式(五)或式(六)结构的配体，合成产物收率相对较高。
本发明实验过程中偶然发现利用氮原子邻位有一个或多个取代基的双齿氮配体作为配体，配合反应底物，能够通过配体结构调控反应的区域选择性来一步反应得到β2-氨基酸衍生物。实验中也尝试采用氮原子邻位不含有取代基的双齿氮配体，但是目标产物收率小于5％。可能的原因是配体邻位有取代基之后使得反应的启动模式发生了改变，由原来的自由基对烯烃的加成启动变为现在的由芳基卤代物对烯烃的Heck反应启动，从而控制了反应的区域选择性，得到β2-氨基酸衍生物。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (8)

1.一种β2-氨基酸衍生物的制备方法，其特征在于，在溶剂和配体存在条件下，以式(二)所示的α-氨甲基硅、式(三)所示的烯烃和式(四)所示的芳基卤代物或杂芳基卤代物为原料，在保护气体的保护、光照以及光催化剂/过渡金属催化剂的协同催化作用下，充分反应后经分离提纯得到式(一)所示的β2-氨基酸衍生物；反应式如下：
其中，R1、R2各自独立地选自下列之一：C1～C25的烷基、C3～C10的环烷基、C6～C20的芳基、C3～C20的杂芳基、C6～C20的取代芳基、C3～C20的取代杂芳基、C2～C10的烯基；或者
R1、R2与其相邻的氮原子一起形成3～7元环，除该氮原子外，所述3～7元环中包含或不包含额外的杂原子和/或环内或环外双键，所述杂原子为N、S或O，所述双键为一个或两个；且所述3～7元环上的碳原子被一个或多个各自独立地选自下列的取代基取代：H原子、C1～C25的烷基、C3～C10的环烷基、C6～C20的芳基、C3～C20的杂芳基、C6～C20的取代芳基、C3～C20的取代杂芳基或C2～C10的烯基；
R3、R4、R5各自独立地选自下列之一：C1～C10的烷基、C6～C20的芳基、C6～C20的取代芳基；
EWG选自C1-C50的吸电子基团；
Ar为C6～C30的芳基或C3～C30的芳杂基；
X选自卤素或拟卤化合物；
所述配体选自如式(五)、式(六)、式(七)、式(八)和式(九)中所示的结构式中的一种或多种：
其中，R6、R7、R8和R9各自独立地选自下列之一：C1～C25的烷基、C6～C20的芳基、C3～C20的杂芳基、C6～C20的取代芳基、C3～C20的取代杂芳基、C2～C10的烯基、氟、氯、溴、氰基、乙酰基、醛基、酯基、乙酰氧基和C1～C5的烷氧基；
所述溶剂为N,N’-二甲基甲酰胺、N,N’-二甲基乙酰胺和N-甲基吡咯烷酮中的一种或多种；
所述光催化剂为Ir(ppy)2(bpy)PF6、Ru(bpy)3(PF6)2、Ir[dF(CF3)ppy]2(dtbbpy)PF6、fac-Ir(ppy)3、Ir[dF(CF3)ppy]2(bpy)PF6、Ir(ppy)2(dtbpy)PF6、Ir[dFppy]2(dtbbpy)PF6或4CzIPN；所述过渡金属催化剂为NiCl2、Ni(dppf)Cl2、NiBr2、NiCl2·glyme和NiBr2·glyme中的一种或多种。
2.如权利要求1所述的制备方法，其特征在于，所述R1、R2各自独立地选自C1～C10的烷基、C6-C10的芳基、C3-C10的杂芳基、C6-C10的取代芳基、C3-C10的取代杂芳基；
所述R3、R4、R5各自独立选自下列之一：C1～C5的烷基、C6-C10芳基、C6-C10取代芳基。
3.如权利要求1所述的制备方法，其特征在于，所述EWG选自C1-C50的酯基、C1-C50的酰胺基或氰基。
4.如权利要求1所述的制备方法，其特征在于，所述Ar为C6～C20的芳基或C3～C20的芳杂基。
5.如权利要求1所述的制备方法，其特征在于，所述X选自溴、碘、氯、三氟甲磺酸酯、对甲苯磺酸酯和甲磺酸酯。
6.如权利要求1所述的制备方法，其特征在于，所述配体选自如式(五)和式(六)中所示的结构中的一种或多种。
7.如权利要求1所述的制备方法，其特征在于，式(二)所示的α-氨甲基硅、式(三)所示的烯烃和式(四)所示的芳基卤代物或杂芳基卤代物的摩尔比为(1～10)：1：(1～10)。
8.如权利要求1所述的制备方法，其特征在于，所述光照为可见光照射。
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