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Stereoselective Synthesis of 1,2,3‐Trisubstituted 1,3‐Dienes through Novel [3,3]‐Sigmatropic Rearrangements in α‐Allenic Methanesulfonates: Application to the Preparation of Fused Tricyclic Systems by Tandem Rearrangement/Diels−Alder Reaction
Author(s) -
Alcaide Benito,
Almendros Pedro,
Aragoncillo Cristina,
Redondo María C.
Publication year - 2005
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.200400527
Subject(s) - chemistry , sigmatropic reaction , stereoselectivity , domino , intramolecular force , cascade reaction , tandem , cope rearrangement , amine gas treating , diels–alder reaction , organic chemistry , stereochemistry , combinatorial chemistry , medicinal chemistry , catalysis , materials science , composite material
An unprecedented stereoselective and general synthesis of 1,2,3‐trisubstituted 1,3‐dienes from α‐allenols just by treatment with a methanesulfonyl chloride/tertiary amine system has been developed. This transformation might be tentatively explained in terms of a migration of the methanesulfonyl group in the initially formed α‐allenic methanesulfonate to give the corresponding mesyloxy‐diene through a [3,3]‐sigmatropic rearrangement. This reactivity pattern was incorporated into a domino process, allowing the development of a novel one‐pot synthetic strategy for the preparation of fused tricycles from monocyclic allenols, masked functionalized dienes, when subjected to a domino allenol transposition/intramolecular Diels−Alder reaction process. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)