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Chiral Induction in Intramolecular Rhodium‐Catalyzed [2+2+2] Cycloadditions of Optically Active Allene–ene/yne–allene Substrates
Author(s) -
Haraburda Ewelina,
Fernández Martí,
Gifreu Anna,
Garcia Jordi,
Parella Teodor,
PlaQuintana Anna,
Roglans Anna
Publication year - 2017
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201600613
Subject(s) - allene , chemistry , cycloaddition , moiety , diastereomer , stereoselectivity , intramolecular force , stereochemistry , catalysis , organic chemistry
Abstract Allene‐yne‐allene and allene‐ene‐allene N ‐tosyl‐linked substrates with two chiral centres in the α‐position of the allene moiety were satisfactorily prepared starting both from racemic and chiral propargylic alcohols. The Wilkinson's complex‐catalyzed [2+2+2] cycloaddition reaction of these substrates was evaluated. In the case of enantiomerically pure bisallenes, high stereoselectivity was observed, giving a diastereomerically pure cycloadduct. The chirality of starting bisallene substrates can be completely transferred to the cycloadducts, representing an atom‐economical and enantiospecific process for the construction of fused polycycles. However, when reacting an oxygen‐linked allene‐ene‐allene substrate, the stereoselectivity decreased and two diastereoisomers were formed. A detailed characterization study of the resulting cycloadducts allowed us to identify the enantioisomer generated in the cycloaddition.