A Copper(I)-Catalyzed Radical-Relay Reaction Enabling the Intermolecular 1,2-Alkylborylation of Unactivated Olefins
- 30 March 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 143 (13), 5260-5268
- https://doi.org/10.1021/jacs.1c02050
Abstract
The first catalytic intermolecular 1,2-alkylborylation reaction via a radical-relay mechanism between unactivated olefins, bis(pinacolato)diboron, and an alkyl electrophile is reported. Successful implementation of this method requires that the competing boryl substitution of the alkyl electrophile is retarded to facilitate the radical relay. This challenge was overcome using electronically or sterically demanding alkyl electrophiles, which results in the simultaneous and highly regioselective introduction of a gem-difluoro, monofluoro, tertiary, or secondary alkyl group and a boryl group across the C═C double bond.Funding Information
- Ministry of Education, Culture, Sports, Science and Technology
- Core Research for Evolutional Science and Technology (JPMJCR19R1)
- Japan Society for the Promotion of Science (17H06370, 18H03907, 18J20858, 19K15547, 20H04795)
This publication has 53 references indexed in Scilit:
- Recent developments in nickel-catalyzed intermolecular dicarbofunctionalization of alkenesChemical Science, 2020
- Three-Component Olefin Dicarbofunctionalization Enabled by Nickel/Photoredox Dual CatalysisJournal of the American Chemical Society, 2019
- Ni-Catalyzed Reductive Dicarbofunctionalization of Nonactivated Alkenes: Scope and Mechanistic InsightsJournal of the American Chemical Society, 2019
- Catalytic cascade reactions by radical relayChemical Society Reviews, 2019
- Copper-Catalyzed Radical Relay for Asymmetric Radical TransformationsAccounts of Chemical Research, 2018
- Transition‐Metal‐Catalyzed Three‐Component Difunctionalizations of AlkenesChemistry – An Asian Journal, 2018
- Transition Metal‐Catalyzed Dicarbofunctionalization of Unactivated OlefinsThe Chemical Record, 2018
- Recent Advances in Radical Difunctionalization of Simple AlkenesEuropean Journal of Organic Chemistry, 2017
- A general alkyl-alkyl cross-coupling enabled by redox-active esters and alkylzinc reagentsScience, 2016
- Copper-Catalyzed Intermolecular Trifluoromethylarylation of Alkenes: Mutual Activation of Arylboronic Acid and CF3+ ReagentJournal of the American Chemical Society, 2014