一种新的烯酰胺区域选择性Heck乙烯基化反应。用于快速分离的含氟标记双齿配体的合成与研究。

A new regioselective Heck vinylation with enamides. Synthesis and investigation of fluorous-tagged bidentate ligands for fast separation.

作者信息

Vallin Karl S A, Zhang Qisheng, Larhed Mats, Curran Dennis P, Hallberg Anders

机构信息

Department of Organic Pharmaceutical Chemistry, Uppsala University, BMC, Box-574, SE-751 23 Uppsala, Sweden.

出版信息

J Org Chem. 2003 Aug 22;68(17):6639-45. doi: 10.1021/jo034265i.

DOI:10.1021/jo034265i

PMID:12919028

Abstract

Internal ligand-controlled Heck vinylations of enamides were performed with high regioselectivity and delivered moderate to good yields of dienamides. Controlled heating by microwave irradiation accelerated the palladium-catalyzed reactions, and full conversions were achieved after reaction times of only 15-30 min. New bidentate fluorous-tagged 1,3-bis(diphenylphosphino)propane ligands (F-dppp's) were synthesized and examined. The cationic vinylations of the enamides with F-dppp ligands rendered essentially the same alpha-selectivity and catalytic activity as in those vinylations where nonfluorous ligands were employed. After reaction, the fluorous-tagged ligand material was easily removed by convenient solid fluorous phase separation. The high selectivity, simplicity, and generality of the experimental procedure should make this approach to 2-acylamino-1,3-butadienes attractive.

摘要

烯酰胺的分子内配体控制的Heck乙烯基化反应具有高区域选择性，能得到中等至良好产率的二烯酰胺。通过微波辐射控制加热加速了钯催化反应，仅15 - 30分钟的反应时间后即可实现完全转化。合成并研究了新型双齿含氟标记的1,3 - 双（二苯基膦基）丙烷配体（F - dppp）。烯酰胺与F - dppp配体的阳离子乙烯基化反应与使用非含氟配体的乙烯基化反应具有基本相同的α选择性和催化活性。反应后，通过便捷的固相氟相分离可轻松除去含氟标记的配体材料。该实验方法的高选择性、简单性和通用性应使这种制备2 - 酰基氨基 - 1,3 - 丁二烯的方法具有吸引力。