文献类型：期刊文献

英文题名：Ligand-and Additive-Controlled Pd-Catalyzed Aminocarbonylation of Alkynes with Aminophenols: Highly Chemo-and Regioselective Synthesis of α,β-Unsaturated

作者：Sha, Feng[1,2,3];Alper, Howard[3]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Key Lab Adv Mat, Meilong Rd 130, Shanghai, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem & Mol Engn, Inst Fine Chem, Meilong Rd 130, Shanghai, Peoples R China;[3]Univ Ottawa, Dept Chem & Biomol Sci, Ctr Catalysis Res & Innovat, 10 Marie Curie, Ottawa, ON K1N 6N5, Canada

年份：2017

卷号：7

期号：3

起止页码：2220

外文期刊名：ACS CATALYSIS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000395726500087)】；

基金：We are grateful to the Natural Sciences and Engineering Research Council of Canada for support of this research.

语种：英文

外文关键词：aminocarbonylation; alpha,beta-unsaturated amides; aminophenols; alkynes; regioselectivity

摘要：This work describes the chemo-and regioselective direct aminocarbonylation of alkynes and aminophenols to form hydroxy-substituted alpha,beta-unsaturated amides in good to excellent yields. The latter are valuable compounds in pharmaceuticals and natural products. By a simple choice of different ligands and additives, branched or linear isomers could be selectively formed in excellent regioselectivity. Using a combination of boronic acid and 5-chlorosalicylic acid ("BCSA") as the additives, linear amides were obtained in high yields and selectivities using 1,2-bis(di-tert-butylphosphinomethyl)benzene (DTBPMB) as the ligand. On the other hand, branched amides could be approached by introducing 1,3-bis(diphenylphosphino)propane as the ligand and p-TsOH center dot H2O as the additive. In addition to the hydroxyl group, other functional substituents, such as carboxyl and vinyl groups, could also be tolerated using this method. As an application of this strategy, the natural product avenanthramide A could be synthesized directly in 84% yield and in 99% regioselectivity via the carbonylation of 2-amino-S-hydroxybenzoic acid and 4-ethynylphenol. Further studies show that the ligands and the additives are keys to good yields and selectivities.