铑（I）催化通过四方氧化锡（II）的氧化还原金属转移实现羰基烯丙基化与炔丙基化反应

Rhodium(I)-catalyzed carbonyl allenylation versus propargylation via redox transmetalation across tetragonal tin(II) oxide.

作者信息

Banerjee Moloy, Roy Sujit

机构信息

Organometallics & Catalysis Laboratory, Chemistry Department, Indian Institute of Technology, Kharagpur 721302, India.

出版信息

Org Lett. 2004 Jun 24;6(13):2137-40. doi: 10.1021/ol0493352.

DOI:10.1021/ol0493352

PMID:15200304

Abstract

[reaction: see text] A reagent combination of beta-SnO and catalytic Rh(COD)Cl in THF-H(2)O promotes the reaction of propargyl bromides and aldehydes and directs the regioselectivity toward the formation of either allenic alcohols or homopropargylic alcohols. This highly regioselective either/or transformation proceeds via a transmetalation from rhodium to tin, in which metallotropic rearrangement between a propargylmetal and allenylmetal is arrested.

摘要

[反应：见正文] β-SnO与催化量的[Rh(COD)Cl]₂在四氢呋喃-水体系中的试剂组合促进了炔丙基溴与醛的反应，并引导区域选择性地生成联烯醇或高炔丙醇。这种高度区域选择性的“二者择一”转化通过从铑到锡的金属转移进行，其中炔丙基金属和联烯基金属之间的金属重排被阻止。