Synthesis and Molecular Structure of β-Phosphinoyl Carboxamides: An Unexpected Case of Chiral Discrimination of Hydrogen-Bonded Dimers in the Solid State

被引：13

作者：

Alajarin, Mateo ^{[1
]}

Lopez-Leonardo, Carmen ^{[1
]}

Alvarez-Garcia, Angel ^{[1
]}

Llamas-Lorente, Pilar ^{[1
]}

Sanchez-Andrada, Pilar ^{[1
]}

Berna, Jose ^{[1
]}

Pastor, Aurelia ^{[1
]}

Bautista, Delia ^{[2
]}

Jones, Peter G. ^{[3
]}

机构：

[1] Univ Murcia, Fac Quim, Dept Quim Organ, E-30100 Murcia, Spain

[2] Univ Murcia, SAI, E-30100 Murcia, Spain

[3] Tech Univ Carolo Wilhelmina Braunschweig, Inst Anorgan & Analyt Chem, D-38023 Braunschweig, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2010年 / 16卷 / 12期

关键词：

chiral recognition; dimerization; hydrogen bonds; phosphorus; solid-state structures; RECOGNITION; CHEMISTRY; LIGANDS; AMINOPHOSPHANES; KETENIMINES; N-ACYL-4-ACYLOXY-BETA-LACTAMS; 1,3-OXAZIN-6-ONES; CONVERSION; INCLUSION; MECHANISM;

D O I：

10.1002/chem.200901845

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A series of N,P,P-trisubstituted aminophosphanes react with diphenylcyclopropenone to afford an easily separable mixture of two diastereomeric alpha,beta-diphenyl-beta-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 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.

引用

页码：3728 / 3735

页数：8

共 55 条

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