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Regioselective Alkylation of the Polyfunctional Nucleophile 1‐(Methylthio)‐3‐triethylsilyloxypentadienyllithium
Author(s) -
Oppolzer Wolfgang,
Snowden Roger L.,
Briner Paul H.
Publication year - 1981
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19810640706
Subject(s) - chemistry , regioselectivity , deprotonation , alkylation , nucleophile , intramolecular force , cleavage (geology) , sulfoxide , enone , medicinal chemistry , organic chemistry , catalysis , ion , geotechnical engineering , fracture (geology) , engineering
γ‐Selective sulfenylation of the triethysilyloxypentadienyllithium 1 gave the versatile alkylthiodene 4 which on successive deprotonation and alkylation furnished with high regioselectivity the γ‐products 6 . Fluoride‐promoted silylether cleavage 6 → 7 may be followed by intramolecular [4 + 2]‐addition 7c → 8 and sulfoxide elimination 8 → 9 . The conversions 7b → 12 and 7a → 17 demonstrate the feasibility of 5 to serve as an equivalent of the hypothetical β‐deprotonated divinylketone 13 whose two enone units may be unmasked separately.