同时带有(2S,3S)-双(膦基甲基)和7-顺式氧官能团的对映体纯降冰片烷配体的制备及其在铑催化不对称氢化反应中的应用

Preparation of enantiopure norbornane ligands bearing both (2S,3S)-bis(phosphinomethyl) and 7-syn-oxygen functional groups and an application to rhodium-catalyzed asymmetric hydrogenation.

作者信息

Morimoto Toshiaki, Yamazaki Akira, Achiwa Kazuo

机构信息

School of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan.

出版信息

Chem Pharm Bull (Tokyo). 2004 Nov;52(11):1367-71. doi: 10.1248/cpb.52.1367.

DOI:10.1248/cpb.52.1367

PMID:15516766

Abstract

Enantiopure bicyclo[2.2.1]heptane derivatives having both (2S,3S)-bis[(diphenylphosphino)methyl] and 7-syn-oxygen functional groups were synthesized by using diastereoselective Diels-Alder reaction of di-(1R)-menthyl fumarate and 5-trimethylsilylcyclopentadiene followed by silver-promoted stereospecific frame rearrangement of a bromolactone intermediate. Rhodium-catalyzed asymmetric hydrogenations were carried out using the diphosphines as a chiral ligand.

摘要

通过富马酸二-(1R)-薄荷酯与5-三甲基甲硅烷基环戊二烯的非对映选择性狄尔斯-阿尔德反应，随后对溴内酯中间体进行银促进的立体定向骨架重排，合成了同时具有(2S,3S)-双[(二苯基膦基)甲基]和7-顺式氧官能团的对映体纯双环[2.2.1]庚烷衍生物。使用二膦作为手性配体进行铑催化的不对称氢化反应。