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2‐( p ‐Tolylsulfinyl)benzyl Halides as Efficient Precursors of Optically Pure trans ‐2,3‐Disubstituted Aziridines
Author(s) -
Arroyo Yolanda,
Meana Ángela,
SanzTejedor M. Ascensión,
Alonso Inés,
García Ruano José Luis
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201000217
Subject(s) - carbanion , chemistry , electrophile , halide , stereoselectivity , iodide , aryl , sodium iodide , medicinal chemistry , sulfoxide , combinatorial chemistry , organic chemistry , catalysis , alkyl
Aziridination of ( R )‐ N ‐sulfinylaldimines (aryl, heteroaryl and alkenyl derivatives) with 2‐( p ‐tolyl sulfinyl)benzyl iodide in the presence of sodium hexamethyl disilazide takes place with almost complete control of the stereoselectivity (facial and anti / syn ) and with very high yields affording optically pure N ‐sulfinyl trans ‐2,3‐disubstituted aziridines 7 . Simultaneous removal of both C‐ and N ‐ p ‐tolylsulfinyl groups with t BuLi provides the corresponding trans ‐NH aziridines 8 without affecting their optical purity. Some experimental results suggest these processes evolve through benzyl halocarbenoids as intermediates, whereas theoretical calculations support the formation of benzyl carbanions. These results have served for revising the mechanistic aspects of the reactions of substituted 2‐ p ‐tolylsulfinyl benzylcarbanions with electrophiles.