Catalytic Enantioselective Intermolecular Desymmetrization of Azetidines

The first catalytic asymmetric desymmetrization of azetidines is disclosed. Despite the low propensity of azetidine ring opening and challenging stereocontrol, smooth intermolecular reactions were realized with excellent efficiency and enantioselectivity. These were enabled by the suitable combinati...

Full description

Saved in:
Bibliographic Details
Published in:Journal of the American Chemical Society 2015-05, Vol.137 (18), p.5895-5898
Main Authors: Wang, Zhaobin, Sheong, Fu Kit, Sung, Herman H. Y, Williams, Ian D, Lin, Zhenyang, Sun, Jianwei
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:The first catalytic asymmetric desymmetrization of azetidines is disclosed. Despite the low propensity of azetidine ring opening and challenging stereocontrol, smooth intermolecular reactions were realized with excellent efficiency and enantioselectivity. These were enabled by the suitable combination of catalyst, nucleophile, protective group, and reaction conditions. The highly enantioenriched densely functionalized products are versatile precursors to other useful chiral molecules. Mechanistic studies, including DFT calculations, revealed that only one catalyst molecule is involved in the key transition state, though both reactants can be activated. Also, the Curtin–Hammett principle dictates the reaction proceeds via amide nitrogen activation.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.5b03083