关于铃木-宫浦反应和根岸偶联反应与链烯基磷酸酯的研究：在1,1-二取代烯烃合成中的应用。

Investigations on the Suzuki-Miyaura and Negishi couplings with alkenyl phosphates: application to the synthesis of 1,1-disubstituted alkenes.

作者信息

Hansen Anders L, Ebran Jean-Philippe, Gøgsig Thomas M, Skrydstrup Troels

机构信息

The Center for Insoluble Protein Structures (inSPIN), Department of Chemistry and the Interdisciplinary Nanoscience Center, University of Aarhus, Langelandsgade 140, 8000 Aarhus C, Denmark.

出版信息

J Org Chem. 2007 Aug 17;72(17):6464-72. doi: 10.1021/jo070912k. Epub 2007 Jul 14.

DOI:10.1021/jo070912k

PMID:17630802

Abstract

The development of versatile Suzuki-Miyaura and Negishi cross-couplings with nonactivated alkenyl phosphates and aromatic boronic acids or organozinc reagents was achieved in acceptable to good yields. A series of 1,1-disubstituted alkenes were synthesized using a combination of either Ni(COD)2/Cy3P/K3PO4 or Pd2dba3/DPPF in THF. When working with alkenyl electrophiles in metal-catalyzed cross-couplings, this method lends itself as a less costly and more stable alternative to the corresponding triflate or nonaflate derivatives. In addition, initial studies are presented regarding an efficient 1,2-migration under Negishi coupling conditions.

摘要

通过与未活化的链烯基磷酸酯和芳基硼酸或有机锌试剂进行通用的铃木-宫浦和根岸交叉偶联反应，可获得良好至优异的产率。在四氢呋喃中，使用Ni(COD)2/Cy3P/K3PO4或Pd2dba3/DPPF的组合合成了一系列1,1-二取代烯烃。在金属催化的交叉偶联反应中使用链烯基亲电试剂时，该方法是相应三氟甲磺酸酯或九氟甲磺酸酯衍生物的一种成本更低且更稳定的替代方法。此外，还介绍了关于在根岸偶联条件下进行有效1,2-迁移的初步研究。