1,n-Bisborylalkanes via Radical Boron Migration
- 3 May 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 142 (20), 9119-9123
- https://doi.org/10.1021/jacs.0c03058
Abstract
A systematic study of radical boron migration in diboronate complexes to form synthetically valuable 1,n-bisborylalkanes is reported. The boronate complexes are readily generated by reaction of commercial bis(pinacolato)diboron with alkyl Grignard compounds. C-radical generation at defined position with respect to the diboron moiety is either achieved via intermolecular H-abstraction with a CF3-radical or via alkene perfluoroalkyl radical addition. It is shown that radical 1,2- and 1,4-boron migration to provide geminal and 1,3-bisborylalkanes are efficient transformations. The 1,5-boron migration in the homologous series leading to 1,4-bisborylalkanes is also occurring, albeit with lower efficiency. Experimental results are supported by DFT calculations which also reveal the corresponding 1,3-boron migration in such diboronate complexes to be feasible.Keywords
Funding Information
- Alexander von Humboldt-Stiftung
- H2020 European Research Council (692640)
This publication has 53 references indexed in Scilit:
- Radical‐Induced 1,2‐Migrations of Boron Ate ComplexesAdvanced Synthesis & Catalysis, 2019
- α-Borylalkyl radicals: their distinctive reactivity in modern organic synthesisChemical Communications, 2019
- Reactions of organoboron compounds enabled by catalyst-promoted metalate shiftsChemical Society Reviews, 2019
- Radical Reactions of Boron-Ate Complexes Promoting a 1,2-Metallate RearrangementChimia, 2019
- Radical-Polar Crossover Reactions of Dienylboronate Complexes: Synthesis of Functionalized Allylboronic EstersOrganic Letters, 2018
- Synthesis of α-Chiral Ketones and Chiral Alkanes Using Radical Polar Crossover Reactions of Vinyl Boron Ate ComplexesAngewandte Chemie-International Edition, 2018
- Radical-polar crossover reactions of vinylboron ate complexesScience, 2017
- Boron chemistry in a new lightChemical Science, 2015
- Lithiation–Borylation Methodology and Its Application in SynthesisAccounts of Chemical Research, 2014
- Organoboranes as a Source of RadicalsChemical Reviews, 2001