- Metal-catalyzed reactions of organoboronic acids and esters
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Metal-catalyzed B-C and C-C bond-forming reactions of organoboronic acids that have been pursued in the past three decades by our group are summarized in this article. B-C bond-forming reactions for the synthesis of organoboronic acid derivatives include metal-catalyzed addition reactions of pinacolborane or catecholborane (hydroboration), bis(pinacolato)diboron (diboration), and alkylthioboranes (thioboration) to alkenes, alkynes, 1,3-alkadienes, or 1,2-alka-dienes (allenes). Other B-C bond-forming reactions include coupling reactions of pinacolborane or bis(pinacolato)dibor-on for borylation of C-halogen bonds with palladium catalysts and C-H bonds of arenes and alkenes with iridium catalysts. These reactions have provided a convenient new access to aryl-, 1-alkenyl-, allyl-, or benzylboronates. Metal-catalyzed C-C and C-N bond-forming reactions using boronic acid derivatives include synthesis of novel cyclic triolborate salts for palladium- or copper-catalyzed cross-coupling reactions with organic halides or amines, rhodium- or palladium-catalyzed 1,4-addition reactions of arylboronic acids to α,β-unsaturated carbonyl compounds and rhodium-catalyzed addition of aryl- and 1-alkenylboronic acids to aldehydes and imines.
- Miyaura, Norio
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p. 1535 - 1553
(2009/05/06)
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- Iridium-catalyzed vinylic C-H borylation of cyclic vinyl ethers by bis(pinacolato)diboron
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Vinylic C-H borylation of cyclic vinyl ethers by bis(pinacolato)diboron was effectively catalyzed by iridium complexes comprised of 1/2[Ir(OMe)(cod)] 2 and 4,4′-di-tert-butyl-2.2′-bipyridine in hexane or octane to give the corresponding vinylboron compounds in good yields. The reaction of 1,4-dioxene occurred even at room temperature, whereas the reactions of dihydropyran and dihydrofuran derivatives required a temperature above 80 °C. Although dihydropyran and dihydrofuran themselves produced regioisomeric mixtures of α- and β-borylated products, similar substrates possessing substituents at the γ-position selectively underwent borylation at the α-position. Copyright
- Kikuchi, Takao,Takagi, Jun,Ishiyama, Tatsuo,Miyaura, Norio
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p. 664 - 665
(2008/12/21)
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