镍催化的炔烃与环氧化物的还原偶联反应。

Nickel-catalyzed reductive coupling of alkynes and epoxides.

作者信息

Molinaro Carmela, Jamison Timothy F

机构信息

Massachusetts Institute of Technology, Department of Chemistry, Cambridge, MA 02139, USA.

出版信息

J Am Chem Soc. 2003 Jul 9;125(27):8076-7. doi: 10.1021/ja0361401.

DOI:10.1021/ja0361401

PMID:12837057

Abstract

Nickel-catalyzed, intramolecular and intermolecular reductive coupling of alkynes and epoxides affords synthetically useful homoallylic alcohols of defined alkene geometry. Very high regioselectivity is generally observed, and cyclizations proceed with complete selectivity for endo epoxide opening. This catalytic reaction represents the first use of a non-pi-based electrophile in a growing class of nickel-catalyzed, multicomponent coupling reactions, and is the first catalytic method of reductive coupling of alkynes and epoxides that is effective for both intermolecular and intramolecular cases, and mechanistically distinct from these, possibly involving a nickella(II)oxetane.

摘要

镍催化的炔烃与环氧化合物的分子内和分子间还原偶联反应可生成具有特定烯烃几何构型的、对合成有用的高烯丙醇。通常观察到非常高的区域选择性，并且环化反应以完全的内型环氧化合物开环选择性进行。这种催化反应代表了在一类不断发展的镍催化多组分偶联反应中首次使用非π键亲电试剂，并且是炔烃与环氧化合物还原偶联的第一种催化方法，该方法对分子间和分子内情况均有效，且在机理上与这些情况不同，可能涉及镍（II）氧杂环丁烷。