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1,3‐Difunctionalizations of [1.1.1]Propellane via 1,2‐Metallate Rearrangements of Boronate Complexes
Author(s) -
Yu Songjie,
Jing Changcheng,
Noble Adam,
Aggarwal Varinder K.
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201914875
Subject(s) - propellane , chemistry , electrophile , reagent , bicyclic molecule , electrophilic addition , combinatorial chemistry , stereochemistry , computational chemistry , organic chemistry , catalysis
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.