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Reaction of Baylis–Hillman Adducts with Fluorinated Silanes
Author(s) -
Zemtsov Artem A.,
Levin Vitalij V.,
Dilman Alexander D.,
Struchkova Marina I.,
Belyakov Pavel A.,
Tartakovsky Vladimir A.,
Hu Jinbo
Publication year - 2010
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.201001051
Subject(s) - carbanion , chemistry , ketone , adduct , nitrile , allylic rearrangement , nucleophile , silanes , medicinal chemistry , reagent , double bond , addition reaction , nucleophilic addition , organic chemistry , catalysis , silane
Abstract Reactions of acylated Baylis–Hillman adducts bearing nitrile, ester, or ketone groups with C 6 F 5 ‐substituted silicon reagents Me n Si(C 6 F 5 ) 4– n ( n = 1–3) have been studied. The reactions are initiated by Bu 4 NOAc (5 mol‐%) in MeCN or DMF under mild conditions and afford products of allylic substitution of the acetoxy group by the C 6 F 5 carbanion in good yields. Predominant or exclusive formation of one geometrical isomer was observed in all cases ( Z for nitriles, E for esters and ketones). For substrates containing carbonyl groups, nucleophilic attack of the C 6 F 5 carbanion chemoselectively occurred at the C=C bond. Reactions of acylated Baylis–Hillman adducts with Me 3 SiCF 3 were found to be inefficient, as the CF 3 carbanion had the propensity to attack the C=O bond of substrates with ester or ketone substituents.