Base-free nickel-catalyzed hydroboration of simple alkenes with bis(pinacolato)diboron in an alcoholic solvent

Li, Jiang-Fei; Zhen-zhong, Wei; Yong-qiu, Wang; Ye, Mengchun

doi:10.1039/c7gc02282d

Cited by 51 publications

(20 citation statements)

References 65 publications

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“…1 H NMR (300 MHz, CDCl 3 ): δ 7.38–6.97 (m, 2H), 7.10–6.56 (m, 2H), 3.85 (s, 3H), 3.22–2.40 (m, 2H), 1.27 (d, 12H), and 1.24–1.10 (m, 2H); 13 C{ 1 H} NMR (76 MHz, CDCl 3 ): δ 157.4, 132.8, 129.1, 126.7, 120.3, 110.1, 83.0, 55.2, 24.9, and 24.4 ppm; 11 B{ 1 H} NMR (96 MHz, CDCl 3 ): δ 34.09 ppm. The NMR is consistent with literature data …”

Section: Experimental Sectionsupporting

confidence: 91%

“…The NMR is consistent with literature data. 44 4-(2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)ethyl)phenyl Acetate (14g). Prepared according to the general procedure from 4vinylphenyl acetate (1.0 mmol) and 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (HBpin, ∼153.6 mg, 1.2 mmol, 1.2 equiv), purified by flash column chromatography eluting with hexanes/DCM (1:1) to provide the title compound as a colorless oil (104 mg, 0.36 mmol, 36% yield).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Tropylium-Promoted Hydroboration Reactions: Mechanistic Insights Via Experimental and Computational Studies

2021

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Hydroboration reaction of alkynes is one of the most synthetically powerful tools to access organoboron compounds, versatile precursors for cross-coupling chemistry. This type of reaction has traditionally been mediated by transition-metal or main group catalysts. Herein, we report a novel method using tropylium salts, typically known as organic oxidants and Lewis acids, to promote the hydroboration reaction of alkynes. A broad range of vinylboranes can be easily accessed via this metal-free protocol. Similar hydroboration reactions of alkenes and epoxides can also be efficiently catalyzed by the same tropylium catalysts. Experimental studies and DFT calculations suggested that the reaction follows an uncommon mechanistic pathway, which is triggered by the hydride abstraction of pinacolborane with tropylium ion. This is followed by a series of in situ counterion-activated substituent exchanges to generate boron intermediates that promote the hydroboration reaction.

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Section: Experimental Sectionsupporting

confidence: 91%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Tropylium-Promoted Hydroboration Reactions: Mechanistic Insights Via Experimental and Computational Studies

2021

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“…15 6, 136.6, 128.9, 113.6, 83.1, 55.3, 29.1, 24.8 4, 132.8, 129.1, 126.7, 120.3, 110.1, 83.0, 55.2, 24.9, 24.4 The NMR is consistent with literature data. 17 4, 131.2, 129.8, 119.2, 83.2, 29.4, 24.8, 12.8 The NMR is consistent with literature data. 16 6, 129.1, 128.6, 126.5, 63.7, 39.2 ppm.…”

Section: S24supporting

confidence: 88%

Tropylium Salt Promoted Hydroboration Reactions: Mechanistic Insights via Experimental and Computational Studies

Ton¹,

Khanh²,

Nguyên

2021

Preprint

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Hydroboration reaction of alkynes is one of the most synthetically powerful tools to access organoboron compounds, versatile precursors for cross coupling chemistry. This type of reaction has traditionally been mediated by transition metal or main group catalysts. Herein, we report a novel method using tropylium salts, typically known as organic oxidants and Lewis acids, to efficiently promote the hydroboration reaction of alkynes. A broad range of vinylboranes can be easily accessed via this metal-free protocol. Similar hydroboration reactions of alkenes and epoxides can also be efficiently catalyzed by the same tropylium catalysts. Experimental studies and DFT calculations suggested that the reaction follows an uncommon mechanistic paradigm, which is triggered by a hydride abstraction of pinacolborane with tropylium ion. This is followed by a series of <i>in situ</i> counterion-activated substituent exchanges to generate boron intermediates that promote the hydroboration reaction.

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“…Apart from hydroborations with HBPin, a green protocol for the Ni-catalyzed formal "anti-Markovnikov" hydroboration using with B 2 Pin 2 was developed. [235] The catalytic system involved Ni(COD) 2 and tBu 3 P; methanol was used as the hydrogen source (Table 9, entry 13). The reaction commenced with oxidative addition of B 2 Pin 2 and further alkene insertion into the [Ni]À Bpin species resuting in 1,2-substituted boronated organonickel intermediate.…”

Section: Recent Advances In Alkene Hydroborationmentioning

confidence: 99%

Saturated Boronic Acids, Boronates, and Trifluoroborates: An Update on Their Synthetic and Medicinal Chemistry

Volochnyuk

Gorlova

Grygorenko

2021

Chemistry A European J

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This review discusses recent advances in the chemistry of saturated boronic acids, boronates, and trifluoroborates. Applications of the title compounds in the design of boron-containing drugs are surveyed, with special emphasis on α-amino boronic derivatives. A general overview of saturated boronic compounds as modern tools to construct C(sp 3 )À C and C(sp 3 )-heteroatom bonds is given, including recent developments in the Suzuki-Miyaura and Chan-Lam cross-couplings, single-electron-transfer processes including metallo-and organocatalytic photoredox reactions, and transformations of boron "ate" complexes. Finally, an attempt to summarize the current state of the art in the synthesis of saturated boronic acids, boronates, and trifluoroborates is made, with a brief mention of the "classical" methods (transmetallation of organolithium/magnesium reagents with boron species, anti-Markovnikov hydroboration of alkenes, and the modification of alkenyl boron compounds) and a special focus on recent methodologies (boronation of alkyl (pseudo)halides, derivatives of carboxylic acids, alcohols, and primary amines, boronative CÀ H activation, novel approaches to alkene hydroboration, and 1,2-metallate-type rearrangements).

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Base-free nickel-catalyzed hydroboration of simple alkenes with bis(pinacolato)diboron in an alcoholic solvent

Abstract: A base-free nickel-catalyzed hydroboration of unreactive simple alkenes with bis(pinacolato)diboron using methanol as the hydride source under mild conditions has been developed.

Cited by 51 publications

References 65 publications

Tropylium-Promoted Hydroboration Reactions: Mechanistic Insights Via Experimental and Computational Studies

Tropylium-Promoted Hydroboration Reactions: Mechanistic Insights Via Experimental and Computational Studies

Tropylium Salt Promoted Hydroboration Reactions: Mechanistic Insights via Experimental and Computational Studies

Saturated Boronic Acids, Boronates, and Trifluoroborates: An Update on Their Synthetic and Medicinal Chemistry

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