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Chiral Induction in Intramolecular Rhodium-Catalyzed [2+2+2] Cycloadditions of Optically Active Allene-ene/yne-allene Substrates

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

Financial support from the Spanish Ministry of Education and Science (MINECO) (Projects No.: CTQ2014–54306-P, CTQ2015-64436-P and SAF2014-52223-C2-1-R) and the DIUE of the Generalitat de Catalunya (Project No.: 2014SGR931 and predoctoral grant to M.F.) are acknowledged. Thanks are due to UdG for a predoctoral grant to E.H.

info:eu-repo/grantAgreement/MINECO//CTQ2014-54306-P/ES/ESTUDIOS TEORICO-EXPERIMENTALES DE CICLACIONES CATALIZADAS POR METALES DE TRANSICION. NUEVOS DESARROLLOS EN AROMATICIDAD, FUNCIONALES DE LA DENSIDAD Y QUIMICA SUPRAMOLECULAR/

Wiley

Manager: Ministerio de Economía y Competitividad (Espanya)
Author: Haraburda, Ewelina
Fernández Wang, Martí
Gifreu, Anna
Garcia, Jordi
Parella Coll, Teodor
Pla i Quintana, Anna
Roglans i Ribas, Anna
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
Financial support from the Spanish Ministry of Education and Science (MINECO) (Projects No.: CTQ2014–54306-P, CTQ2015-64436-P and SAF2014-52223-C2-1-R) and the DIUE of the Generalitat de Catalunya (Project No.: 2014SGR931 and predoctoral grant to M.F.) are acknowledged. Thanks are due to UdG for a predoctoral grant to E.H.
Format: application/pdf
Document access: http://hdl.handle.net/10256/13482
Language: eng
Publisher: Wiley
Collection: info:eu-repo/semantics/altIdentifier/doi/10.1002/adsc.201600613
info:eu-repo/semantics/altIdentifier/issn/1615-4150
info:eu-repo/semantics/altIdentifier/eissn/1615-4169
Is part of: info:eu-repo/grantAgreement/MINECO//CTQ2014-54306-P/ES/ESTUDIOS TEORICO-EXPERIMENTALES DE CICLACIONES CATALIZADAS POR METALES DE TRANSICION. NUEVOS DESARROLLOS EN AROMATICIDAD, FUNCIONALES DE LA DENSIDAD Y QUIMICA SUPRAMOLECULAR/
Rights: Tots els drets reservats
Subject: Ciclització (Química)
Ring formation (Chemistry)
Al·lens
Allenes
Rodi
Rhodium
Title: Chiral Induction in Intramolecular Rhodium-Catalyzed [2+2+2] Cycloadditions of Optically Active Allene-ene/yne-allene Substrates
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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