Unsaturated Nitriles:  Stereoselective MgO Eliminations

α,β-Unsaturated nitriles are readily synthesized by eliminating MgO from β-hydroxynitriles. Deprotonating acyclic, and cyclic, β-hydroxynitriles with excess MeMgCl smoothly generates dianion intermediates that eject MgO with concurrent formation of α,β-unsaturated nitriles. Alternatively, sequential...

Full description

Saved in:
Bibliographic Details
Published in:Journal of organic chemistry 2002-05, Vol.67 (11), p.3668-3672
Main Authors: Fleming, Fraser F, Shook, Brian C
Format: Article
Language:English
Subjects:
Aldehydes - chemistry
Aliphatic compounds
Chemistry
Exact sciences and technology
Ketones - chemistry
Magnesium Oxide - chemistry
Nitriles - chemical synthesis
Organic chemistry
Preparations and properties
Stereoisomerism
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:α,β-Unsaturated nitriles are readily synthesized by eliminating MgO from β-hydroxynitriles. Deprotonating acyclic, and cyclic, β-hydroxynitriles with excess MeMgCl smoothly generates dianion intermediates that eject MgO with concurrent formation of α,β-unsaturated nitriles. Alternatively, sequential addition of lithioacetonitrile and MgBr2 to aldehydes and ketones generates magnesium alkoxides in situ that eliminate MgO upon addition of MeMgCl. The MeMgCl-induced MgO eliminations smoothly generate α,β-unsaturated nitriles from hindered ketones that are otherwise difficult to synthesize.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo0162944