TY - JOUR
T1 - Silylene-mediated polarity reversal of dienoates
T2 - Additions of dienoates to aldehydes at the δ-position to form trans-dioxasilacyclononenes
AU - Ventocilla, Christian C.
AU - Woerpel, K. A.
PY - 2011/1/26
Y1 - 2011/1/26
N2 - Silylene transfer to αβ,γ,δ-unsaturated carbonyl compounds produced oxasilacyclopentenes that underwent thermal additions to aldehydes to produce trans-dioxasilacyclononenes as single stereoisomers. This reaction, which converts the δ-position of the unsaturated carbonyl compound into a nucleophilic center, represents an inversion of polarity from the normal pattern of reactivity. The stereospecificity of the reaction suggests that the addition to aldehydes occurred through a closed, chairlike six-membered transition state. This reaction can be used to prepare enantiomerically pure materials by the use of chiral auxiliaries to control the formation of the oxasilacyclopentenes. Functionalization of the resulting trans-cycloalkene occurred with complete stereoselectively.
AB - Silylene transfer to αβ,γ,δ-unsaturated carbonyl compounds produced oxasilacyclopentenes that underwent thermal additions to aldehydes to produce trans-dioxasilacyclononenes as single stereoisomers. This reaction, which converts the δ-position of the unsaturated carbonyl compound into a nucleophilic center, represents an inversion of polarity from the normal pattern of reactivity. The stereospecificity of the reaction suggests that the addition to aldehydes occurred through a closed, chairlike six-membered transition state. This reaction can be used to prepare enantiomerically pure materials by the use of chiral auxiliaries to control the formation of the oxasilacyclopentenes. Functionalization of the resulting trans-cycloalkene occurred with complete stereoselectively.
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U2 - 10.1021/ja109631z
DO - 10.1021/ja109631z
M3 - Article
C2 - 21166421
AN - SCOPUS:79851499673
SN - 0002-7863
VL - 133
SP - 406
EP - 408
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 3
ER -