α-磺酰基碳负离子与手性双恶唑啉的催化及高对映选择性反应。

Catalytic and highly enantioselective reactions of alpha-sulfonyl carbanions with chiral bis(oxazoline)s.

作者信息

Nakamura Shuichi, Hirata Norimune, Yamada Ryusuke, Kita Takeshi, Shibata Norio, Toru Takeshi

机构信息

Department of Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Nagoya 466-8555, Japan.

出版信息

Chemistry. 2008;14(18):5519-27. doi: 10.1002/chem.200800221.

DOI:10.1002/chem.200800221

PMID:18461587

Abstract

The enantioselective reactions of lithiated benzyl trifluoromethyl sulfones with a substoichiometric amount of a bis(oxazoline) and various aldehydes is disclosed. The products were formed with excellent diastereo- and enantioselectivities. Fluorination of the sulfone with N-fluorobenzenesulfonimide and a stoichiometric amount of a bis(oxazoline) gave products with extremely high enantioselectivities (up to 99% ee; ee=enantiomeric excess). The enantioselective reaction was confirmed to proceed through a dynamic thermodynamic resolution pathway.

摘要

公开了锂化苄基三氟甲基砜与亚化学计量的双恶唑啉及各种醛的对映选择性反应。产物以优异的非对映和对映选择性形成。用N-氟苯磺酰亚胺和化学计量的双恶唑啉对砜进行氟化，得到对映选择性极高的产物（对映体过量高达99%；ee = 对映体过量）。证实该对映选择性反应通过动态热力学拆分途径进行。