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1,2-Boron Shifts of β-Boryl Radicals Generated from Bis-boronic Esters Using Photoredox Catalysis

Research output: Contribution to journalArticle

Original languageEnglish
Pages (from-to)14104-14109
Number of pages6
JournalJournal of the American Chemical Society
Volume141
Issue number36
Early online date28 Aug 2019
DOIs
DateAccepted/In press - 16 Jul 2019
DateE-pub ahead of print - 28 Aug 2019
DatePublished (current) - 11 Sep 2019

Abstract

1,2-Bis-boronic esters are versatile intermediates that enable the rapid elaboration of simple alkene precursors. Previous reports on their selective mono-functionalization have targeted the most accessible position, retaining the more hindered secondary boronic ester. In contrast, we have found that photoredox-catalyzed mono-deboronation generates primary β-boryl radicals that undergo rapid 1,2-boron shift to form thermodynamically favored secondary radicals, allowing for selective transformation of the more hindered boronic ester. The pivotal 1,2-boron shift, which has been demonstrated to be stereoretentive, enables access to a wide range of functionalized boronic esters and has been applied to highly diastereoselective fragmentation and transannular cyclization reactions. Furthermore, its generality has been shown in a radical cascade reaction with an allylboronic ester.

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    Rights statement: This is the author accepted manuscript (AAM). The final published version (version of record) is available online via American Chemical Society at https://pubs.acs.org/doi/10.1021/jacs.9b07564. Please refer to any applicable terms of use of the publisher.

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