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Regio‐ and Stereospecific Cleavage of Stannyloxiranes with Lithium Diphenylphosphide
Author(s) -
GonzálezNogal Ana M.,
Cuadrado Purificación,
Sarmentero M. Angeles
Publication year - 2009
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200800984
Subject(s) - silylation , chemistry , synthon , regioselectivity , stereospecificity , enol , tin , lithium (medication) , medicinal chemistry , cleavage (geology) , organic chemistry , stereochemistry , catalysis , medicine , endocrinology , geotechnical engineering , fracture (geology) , engineering
Unsubstituted or C ‐substituted stannyloxiranes reactedstereospecifically with lithium diphenylphosphide to give either β‐hydroxyphosphane oxides resulting from α‐opening or β‐phosphanyl ketones by β‐opening. Furthermore, the reactivities of distannyloxiranes depend on their configurations. The cis isomers afforded the corresponding α,β‐diphosphanyl alcohols, while the trans isomers were shown to be unreactive. On the other hand, the regiochemistry of the ring‐opening from β‐silyl‐stannyloxiranes is controlled by the tin group and, depending on the nature of the silyl group, led either to stereodefined β‐silylated vinylphosphane oxides or to β‐stannyl silyl enol ethers. Finally, the gem ‐silyl‐stannyloxiranes underwent β‐opening to give mixtures of β‐phosphanyl acylsilanes and silyl enol ethers. All compounds are interesting synthons of great versatility in organic chemistry.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)