Open AccessRationalization of the stereochemistry of an addition of dialkyl phosphites to certain chiral aldimines: The experimental and theoretical approach
Author(s) -
Nazarski Ryszard B.,
Lewkowski Jarosław A.,
Skowroński Romuald
Publication year - 2002
Publication title -
heteroatom chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.283
H-Index - 42
eISSN - 1098-1071
pISSN - 1042-7163
DOI - 10.1002/hc.10005
Subject(s) - chemistry , stereocenter , heteroatom , mndo , diastereomer , furfural , alkane stereochemistry , aldimine , computational chemistry , stereochemistry , organic chemistry , enantioselective synthesis , crystal structure , catalysis , molecule , alkyl
The absolute configuration of an α‐P stereogenic center in two diastereomeric O,O‐dialkyl α‐aminophosphonates ( 3 ), arising from an induced 1,3‐asymmetric phosphite addition to the CN bond of furfural‐derived Schiff bases ( 1 ), was established from single product 1 H NMR data. Such spectra were interpreted with anisotropic shielding in relation to the AM1 and MNDO/d structures of 3 ; the former ones turned out to be closer to the obtained experimental results ( 1 H NMR spectra of 3 , crystallographic database study). Since favored 3‐21G geometries of starting imines 1 were modeled as well, it was inferred that a stereochemical outcome of this reaction is governed by Cram selectivity. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:120–125, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10005