A Copper(I)-Catalyzed Radical-Relay Reaction Enabling the Intermolecular 1,2-Alkylborylation of Unactivated Olefins
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 electrophil...
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| Published in: | Journal of the American Chemical Society Vol. 143; no. 13; pp. 5260 - 5268 |
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| Main Authors: | , , , , |
| Format: | Journal Article |
| Language: | English |
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American Chemical Society
07-04-2021
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| 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 CC double bond. |
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| AbstractList | 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
-difluoro, monofluoro, tertiary, or secondary alkyl group and a boryl group across the C═C double bond. 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 CC double bond. |
| Author | Kubota, Koji Oyama, Natsuki Akiyama, Sota Ito, Hajime Endo, Tsubura |
| AuthorAffiliation | Institute for Chemical Reaction Design and Discovery (WPI-ICReDD) Hokkaido University Division of Applied Chemistry, Graduate School of Engineering |
| AuthorAffiliation_xml | – name: Institute for Chemical Reaction Design and Discovery (WPI-ICReDD) – name: Hokkaido University – name: Division of Applied Chemistry, Graduate School of Engineering |
| Author_xml | – sequence: 1 givenname: Sota surname: Akiyama fullname: Akiyama, Sota organization: Division of Applied Chemistry, Graduate School of Engineering – sequence: 2 givenname: Natsuki surname: Oyama fullname: Oyama, Natsuki organization: Division of Applied Chemistry, Graduate School of Engineering – sequence: 3 givenname: Tsubura surname: Endo fullname: Endo, Tsubura organization: Division of Applied Chemistry, Graduate School of Engineering – sequence: 4 givenname: Koji orcidid: 0000-0003-1522-291X surname: Kubota fullname: Kubota, Koji organization: Hokkaido University – sequence: 5 givenname: Hajime orcidid: 0000-0003-3852-6721 surname: Ito fullname: Ito, Hajime email: hajito@eng.hokudai.ac.jp organization: Hokkaido University |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/33783204$$D View this record in MEDLINE/PubMed |
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| Title | A Copper(I)-Catalyzed Radical-Relay Reaction Enabling the Intermolecular 1,2-Alkylborylation of Unactivated Olefins |
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