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Synthesis and Molecular Structure of β‐Phosphinoyl Carboxamides: An Unexpected Case of Chiral Discrimination of Hydrogen‐Bonded Dimers in the Solid State
Author(s) -
Alajarín Mateo,
LópezLeonardo Carmen,
ÁlvarezGarcía Ángel,
LlamasLorente Pilar,
SánchezAndrada Pilar,
Berná José,
Pastor Aurelia,
Bautista Delia,
Jones Peter G.
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.200901845
Subject(s) - diastereomer , vicinal , chemistry , substituent , enantiomer , molecule , hydrogen bond , acceptor , hydrogen , hydrogen atom , solid state , crystal structure , nitrogen atom , group (periodic table) , crystallography , stereochemistry , computational chemistry , organic chemistry , physics , condensed matter physics
A series of N , P , P ‐trisubstituted aminophosphanes react with diphenylcyclopropenone to afford an easily separable mixture of two diastereomeric α,β‐diphenyl‐β‐phosphinoyl carboxamides in good yields. X‐ray crystal structures reveal that these compounds associate into dimers, formed from two enantiomeric units linked by two bifurcated hydrogen bonds, whereby the oxygen atom of the phosphoryl group acts as a dual acceptor for the vicinal NH and CH of a carbonyl group of a neighbouring molecule. Studies on the interconversion between diastereomeric phosphinoyl carboxamides in basic solution show that the thermodynamically most stable isomer depends on the nature of the substituent at the nitrogen atom. Simple computational calculations explain this phenomenon.