1, 3‐Difunctionalizations of [1.1.1]Propellane via 1, 2‐Metallate Rearrangements of Boronate Complexes. Issue 10 (28th January 2020)

• Record Type: Journal Article
• Authors: Yu, Songjie; Jing, Changcheng; Noble, Adam; Aggarwal, Varinder K.
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 10(2020)
• Page Start: 3917
• Page End: 3921
• Publication Date: 2020-01-28
• Subjects: [1.1.1]propellane -- bicyclo[1.1.1]pentanes -- borylation -- multicomponent reactions -- Zweifel olefination; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201914875
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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. Abstract : 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.