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 sub...

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Published in:Advanced synthesis & catalysis 2017-02, Vol.359 (3), p.506-512
Main Authors: Haraburda, Ewelina, Fernández, Martí, Gifreu, Anna, Garcia, Jordi, Parella, Teodor, Pla‐Quintana, Anna, Roglans, Anna
Format: Article
Language:English
Subjects:
Alcohols
Allene
Allenes
Catalysis
Chiral induction
Chirality
Ciclització (Química)
Cycloaddition
Optical activity
Polycycle
Rhodium
Ring formation (Chemistry)
Rodi
Stereoselectivity
Substrates
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cited_by cdi_FETCH-LOGICAL-c5353-15cf6c836b0a516c7b2495f038faa845346f31d67dca5569b0528363a9b996f33
cites cdi_FETCH-LOGICAL-c5353-15cf6c836b0a516c7b2495f038faa845346f31d67dca5569b0528363a9b996f33
container_end_page 512
container_issue 3
container_start_page 506
container_title Advanced synthesis & catalysis
container_volume 359
creator Haraburda, Ewelina
Fernández, Martí
Gifreu, Anna
Garcia, Jordi
Parella, Teodor
Pla‐Quintana, Anna
Roglans, Anna
description 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.
doi_str_mv 10.1002/adsc.201600613
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subjects Alcohols
Allene
Allenes
Catalysis
Chiral induction
Chirality
Ciclització (Química)
Cycloaddition
Optical activity
Polycycle
Rhodium
Ring formation (Chemistry)
Rodi
Stereoselectivity
Substrates
title Chiral Induction in Intramolecular Rhodium‐Catalyzed [2+2+2] Cycloadditions of Optically Active Allene–ene/yne–allene Substrates
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