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Transition Metal‐Assisted Transformations of Diversely Functionalized Dienynes
Author(s) -
MarcoContelles José,
Mainetti Emily,
Fensterbank Louis,
Malacria Max
Publication year - 2003
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.200310007
Subject(s) - chemistry , stannane , cycloisomerization , stereocenter , yield (engineering) , stereoselectivity , adduct , trimethylsilyl , catalysis , palladium , organic chemistry , medicinal chemistry , transition metal , enantioselective synthesis , materials science , metallurgy
We report the triphenyltin‐mediated free‐radical cyclization of 4‐ethynyl‐2,6,6‐trimethylocta‐1,7‐dien‐4‐ol ( 1 ) and 4‐ethynyl‐6,6‐dimethylocta‐1,7‐dien‐4‐ol ( 2 ), along with some chemical manipulations of the resulting stannylidene derivatives 3 and 7 . The reaction of intermediates 3 and 7 with BuLi afforded the protodestannylated compounds 5 and 8 , respectively, in good yield, while the reaction of the mixture of adducts 3 and 4 with iodine gave the chloro(diphenyl)stannylidene derivatives 6 and 6′ . The palladium dichloride catalyzed reaction of dienyne 1 with tributyl(trimethylsilyl)stannane has also been described. All these cycloisomerization reactions were highly stereoselective, affording unique isomers at the newly formed stereocenters. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)