在烯烃氢化领域中，重量级“R-SMS-Phos”配体。

Heavyweight "R-SMS-Phos" ligands in the olefins' hydrogenation arena.

机构信息

Laboratory of Organic and Medicinal Chemistry, National Institute of Chemistry, Hajdrihova 19, SI-1001 Ljubljana, Slovenia.

出版信息

Org Lett. 2010 Mar 19;12(6):1296-9. doi: 10.1021/ol100184p.

DOI:10.1021/ol100184p

PMID:20170147

Abstract

A series of enantiopure P-stereogenic 1,2-bis[(o-RO-phenyl)(phenyl)phosphino]ethane (R-SMS-Phos) ligands wherein R = i-Pr, i-Bu, t-Bu, 3-Pen, and CH(2)TMS was assessed in the Rh(I)-catalyzed hydrogenation of an indicative set of olefins. The best performing t-Bu-SMS-Phos ligand was screened against a wide range of representative classes of standard and new olefinic substrates such as dehydroamido esters, dehydro-alpha-amido-phosphonates, enamides, itaconates, acrylates, enol acetates, alpha-phosphonovinyl benzoates, alpha-(2-pyridyl N-oxide)styrenes, and alpha-(1-hydroxyliminoethyl)styrenes. Excellent enantioselectivities and high TOFs were attained under mild conditions.

摘要

一系列对映纯的 P-手性 1,2-双[(o-RO-苯基)(苯基)膦基]乙烷 (R-SMS-Phos) 配体，其中 R = i-Pr、i-Bu、t-Bu、3-Pen 和 CH(2)TMS，在 Rh(I)催化的一系列烯烃的氢化反应中进行了评估。在广泛的代表性标准和新型烯烃底物中，如脱氢酰胺酯、脱氢-α-酰胺膦酸酯、烯胺、衣康酸酯、丙烯酸酯、烯醇乙酸酯、α-膦酰基乙烯基苯甲酸酯、α-(2-吡啶基 N-氧化物)苯乙烯和 α-(1-羟基亚氨基乙烯基)苯乙烯，筛选出性能最佳的 t-Bu-SMS-Phos 配体。在温和的条件下，获得了优异的对映选择性和高的 TOFs。