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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Bibliographic Details
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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Summary: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.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.201600613