Loading…
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...
Saved in:
Published in: | Angewandte Chemie International Edition 2020-03, Vol.59 (10), p.3917-3921 |
---|---|
Main Authors: | , , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
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 |