Catalytic Asymmetric Synthesis of Alkynyl Aziridines: Both Enantiomers of cis‐Aziridines from One Enantiomer of the Catalyst. Issue 43 (9th September 2014)

• Record Type: Journal Article
• Authors: Guan, Yong; López‐Alberca, Maria P.; Lu, Zhenjie; Zhang, Yu; Desai, Aman A.; Patwardhan, Aniruddha P.; Dai, Yijing; Vetticatt, Mathew J.; Wulff, William D.
• Is Part Of: Chemistry. Volume 20:Issue 43(2014)
• Page Start: 13894
• Page End: 13900
• Publication Date: 2014-09-09
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201404587
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Alkynyl aziridines can be obtained from the catalytic asymmetric aziridination (AZ reaction) of alkynyl imines with diazo compounds in high yields and high asymmetric inductions mediated by a chiral boroxinate or BOROX catalyst. In contrast to the AZ reaction with aryl‐ and alkyl‐substituted imines, alkynyl imines react to give <italic>cis</italic>‐substituted aziridines with both diazo esters and diazo acetamides. Remarkably, however, the two diazo compounds give different enantiomers of the <italic>cis</italic>‐aziridine from the same enantiomer of the catalyst. Theoretical considerations of the possible transition states for the enantiogenic step reveal that the switch in enantiomers results from a switch from <italic>Si</italic>‐face to <italic>Re</italic>‐face addition to the imine, which in turn is related to a switch from reaction with an <italic>E</italic>‐imine in the former and a <italic>Z</italic>‐isomer of the imine in the latter.</p> </abstract>