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1,3‐Difunctionalizations of [1.1.1]Propellane via 1,2‐Metallate Rearrangements of Boronate Complexes

1,3‐Disubstituted bicyclo[1.1.1]pentanes (BCPs) are valuable bioisosteres of para‐substituted aromatic rings. The most direct route to these structures is via multicomponent ring‐opening reactions of [1.1.1]propellane. However, challenges associated with these transformations mean that difunctionali...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2020-03, Vol.59 (10), p.3917-3921
Main Authors: Yu, Songjie, Jing, Changcheng, Noble, Adam, Aggarwal, Varinder K.
Format: Article
Language:English
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Summary:1,3‐Disubstituted bicyclo[1.1.1]pentanes (BCPs) are valuable bioisosteres of para‐substituted aromatic rings. The most direct route to these structures is via multicomponent ring‐opening reactions of [1.1.1]propellane. However, challenges associated with these transformations mean that difunctionalized BCPs are more commonly prepared by multistep reaction sequences with BCP‐halide intermediates. Herein, we report three‐ and four‐component 1,3‐difunctionalizations of [1.1.1]propellane with organometallic reagents, organoboronic esters, and a variety of electrophiles. This process is achieved by trapping intermediate BCP‐metal species with boronic esters to form boronate complexes, which are versatile intermediates whose electrophile‐induced 1,2‐metallate rearrangement chemistry enables a broad range of C−C bond‐forming reactions. A modular synthesis of 1,3‐difunctionalized bicyclo[1.1.1]pentanes (BCPs) has been achieved through multicomponent couplings between organometallic reagents, [1.1.1]propellane, and organoboronic esters. By utilizing the versatile 1,2‐metallate rearrangement chemistry of boronate complexes generated in situ, a range of C−C bond‐forming reactions could be performed without the need for transition‐metal catalysis.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201914875