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Enantioselective Preparation, Conformational Analysis and Absolute Configuration of Highly Substituted Aziridines
Author(s) -
Bencivenni Giorgio,
Righi Paolo,
Lunazzi Lodovico,
Ranieri Silvia,
Mancinelli Michele,
Mazzanti Andrea
Publication year - 2015
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.22522
Subject(s) - chemistry , absolute configuration , enantioselective synthesis , circular dichroism , spectral line , computational chemistry , density functional theory , stereochemistry , catalysis , organic chemistry , physics , astronomy
The first example of organocatalytic aziridination reaction of α‐substituted‐α,β‐unsaturated ketones is presented. The reaction was found to be highly enantio‐ and diastereoselective , yielding N ‐tosylated aziridines. Low‐temperature nuclear magnetic resonance (NMR) spectra allowed for the determination of the N ‐inversion barrier, that was found to be quite lower with respect to unsubstituted aziridines. A thorough conformational analysis supported by low‐temperature NMR data allowed for the determination of the absolute configuration of the main stereoisomer by means of time‐dependent Density Functional Theory simulation of the electronic circular dichroism spectra. Chirality 27:875–887, 2015 . © 2015 Wiley Periodicals, Inc.