Usage of the carboxylate leaving group in transition-metal-catalyzed cross-coupling and related reactions

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8 Citations (Scopus)

Abstract

This account describes our recent work on catalytic cross-coupling reactions using carboxylate and carbonate leaving groups in the electrophilic substrate. Some bisphosphine-chelated palladium(O) complexes are effective for the cleavage of benzylic C-O bonds in benzyl carbonates and acetates. This C-O bond cleavage was utilized in catalytic reactions of these benzylic esters; the nucleophilic benzylic substitutions and the crosscoupling reactions with organometallic compounds. Furthermore, vinyl acetate was proved to work as the coupling partner of arylboronates in the presence of [RhCl(cod)] 2 -DPPB. Interestingly, the organoborons react selectively at the position β to the leaving group in the alkenyl ester when the rhodium-catalyzed reaction is conducted in the absence of the bisphosphine.

Original languageEnglish
Pages (from-to)1263-1270
Number of pages8
JournalYuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
Volume69
Issue number11
DOIs
Publication statusPublished - Jan 1 2011

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Carbonates
Transition metals
Esters
Organometallic Compounds
Rhodium
Palladium
Acetates
Substitution reactions
Substrates
vinyl acetate

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

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title = "Usage of the carboxylate leaving group in transition-metal-catalyzed cross-coupling and related reactions",
abstract = "This account describes our recent work on catalytic cross-coupling reactions using carboxylate and carbonate leaving groups in the electrophilic substrate. Some bisphosphine-chelated palladium(O) complexes are effective for the cleavage of benzylic C-O bonds in benzyl carbonates and acetates. This C-O bond cleavage was utilized in catalytic reactions of these benzylic esters; the nucleophilic benzylic substitutions and the crosscoupling reactions with organometallic compounds. Furthermore, vinyl acetate was proved to work as the coupling partner of arylboronates in the presence of [RhCl(cod)] 2 -DPPB. Interestingly, the organoborons react selectively at the position β to the leaving group in the alkenyl ester when the rhodium-catalyzed reaction is conducted in the absence of the bisphosphine.",
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AB - This account describes our recent work on catalytic cross-coupling reactions using carboxylate and carbonate leaving groups in the electrophilic substrate. Some bisphosphine-chelated palladium(O) complexes are effective for the cleavage of benzylic C-O bonds in benzyl carbonates and acetates. This C-O bond cleavage was utilized in catalytic reactions of these benzylic esters; the nucleophilic benzylic substitutions and the crosscoupling reactions with organometallic compounds. Furthermore, vinyl acetate was proved to work as the coupling partner of arylboronates in the presence of [RhCl(cod)] 2 -DPPB. Interestingly, the organoborons react selectively at the position β to the leaving group in the alkenyl ester when the rhodium-catalyzed reaction is conducted in the absence of the bisphosphine.

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