Open AccessStereochemical Studies on the Addition of Allylsilanes to Aldehydes. The SE’ Component
Author(s) -
Scott E. Denmark,
Neil G. Almstead
Publication year - 2019
Publication title -
journal of the mexican chemical society
Language(s) - English
Resource type - Journals
ISSN - 2594-0317
DOI - 10.29356/jmcs.v53i3.1001
Subject(s) - chemistry , aldehyde , deuterium , condensation , component (thermodynamics) , lewis acids and bases , selectivity , fluoride , silicon , stereochemistry , condensation reaction , medicinal chemistry , organic chemistry , catalysis , inorganic chemistry , thermodynamics , physics , quantum mechanics
Model compounds ul-1 and lk-1 have been studied to determine both the position of the silicon electrofuge and the relative orientation of the double bonds in the transition structure of the allylmetal-aldehyde condensation. The use of the deuterium label allows an unbiased assessment of the syn versus anti SE’ pathways. The synthesis of configurational proof of model systems ul-1 and lk-1 are discussed as well as the cyclization of the model system. Cyclization of model 1 was found to proceed with high selectivity via an anti SE’ pathway regardless of the proximal/distal ratio for all Lewis acids studied. Reactions promoted by fluoride ion favored the proximal product, but both syn and anti pathways were observed.