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Copper/Amino Acid Catalyzed Cross-Couplings of Aryl and Vinyl Halides with Nucleophiles
其他题名铜/氨基酸催化的芳基和烯基卤与亲核试剂的偶联反应
Ma DW(马大为); Cai Q(蔡倩)
2008
发表期刊Accounts Chem. Res.
ISSN0001-4842
卷号41期号:11页码:1450-1460
摘要Copper-assisted Ullmann-type coupling reactions are valuable transformations for organic synthesis. Researchers have extensively applied these reactions in both academic and industrial settings. However, two important issues, the high reaction temperatures (normally above 150 degrees C) and the stoichiometric amounts of copper necessary, have greatly limited the reaction scope. To solve these problems, we and other groups have recently explored the use of special ligands to promote these coupling reactions. We first showed that the structure of a-amino acids can accelerate Cu-assisted Ullmann reactions, leading to the coupling reactions of aryl halides and alpha-amino acids at 80-90 degrees C. In response to these encouraging results, we also discovered that an L-proline ligand facilitated the following transformations: (1) coupling of aryl halides with primary amines, cyclic secondary amines, and N-containing heterocycles at 40-90 degrees C; (2) coupling of aryl halides with sulfinic acid salts at 80-95 degrees C; (3) azidation of aryl halides and vinyl halides with sodium azide at 40-95 degrees C; (4) coupling of aryl halides with activated methylene compounds at 25-50 degrees C. In addition, we found that N,N-dimethylglycine as a ligand facilitated Cu-catalyzed biaryl ether formation at 90 degrees C. Moreover, Sonogashira reactions worked in the absence of palladium and phosphine ligands, forming enamides from vinyl halides and amides at temperatures ranging from ambient temperature up to 80 degrees C. Furthermore, we discovered that an ortho-amide group can accelerate some Ullmann-type reactions. This functional group in combination with other ligand effects allowed for aryl amination or biaryl ether formation at ambient temperature. The coupling between aryl halides and activated methylene compounds even proceeded at -45 degrees C to enantioselectively form a quaternary carbon center. Taking advantage of these results, we developed several novel approaches for the synthesis of pharmaceutically important heterocycles: 1,2-disubstituted benzimidazoles, polysubstituted indoles, N-substituted 1,3-dihydrobenzimidazol-2-ones, and substituted 3-acyl oxindoles. Our results demonstrate that an L-proline or N,N-dimethylglycine ligand can facilitate most typical Ullmann-type reactions, with reactions occurring under relatively mild conditions and using only 2-20 mol % copper catalysts. These conveniently available and inexpensive catalytic systems not only accelerate the reactions but also tolerate many more functional groups. Thus, they should find considerable application in organic synthesis.
学科领域金属有机化学
部门归属上海有机所
URL查看原文
收录类别SCI
语种英语
WOS记录号WOS:000261000000004
引用统计
被引频次:767[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://ir.sioc.ac.cn/handle/331003/15563
专题生命有机化学国家重点实验室
通讯作者Ma DW(马大为)
推荐引用方式
GB/T 7714
Ma DW,Cai Q. Copper/Amino Acid Catalyzed Cross-Couplings of Aryl and Vinyl Halides with Nucleophiles[J]. Accounts Chem. Res.,2008,41(11):1450-1460.
APA 马大为,&蔡倩.(2008).Copper/Amino Acid Catalyzed Cross-Couplings of Aryl and Vinyl Halides with Nucleophiles.Accounts Chem. Res.,41(11),1450-1460.
MLA 马大为,et al."Copper/Amino Acid Catalyzed Cross-Couplings of Aryl and Vinyl Halides with Nucleophiles".Accounts Chem. Res. 41.11(2008):1450-1460.
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