A theoretical study of the hydroboration of α,β-unsaturated carbonyl compounds catalyzed by a metal-free complex and subsequent C–C coupling with acetonitrile

Zhu, Ling; Zhang, Lin; Yang, Zixu; Pu, Min; Lei, Ming

doi:10.1039/d1nj02218k

Cited by 3 publications

(3 citation statements)

References 58 publications

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“…The average entropy error ( S err ) of the bimolecular adduction process for the present boron-based systems ( S err = 23.9 cal/mol/K) is similar to that of the transition-metal systems studied by Sakaki et al ( S err = 23.0 cal/mol/K) . The SMD and PCM solvent models have no significant impact on the Whitesides’ method (see Tables S2 and S4), and this method has been extensively applied to other reaction systems. − On the other hand, Martin’s method involves using high pressure ((PCM, P = 1354 atm) M06/TZVP//BP86/SVP) to simulate the condensed-phase situation, and the entropy error varies from 17.7 to 32.7 cal/mol/K, as shown in Table S5, distinguishing it from the Whitesides’ method. The average value of S err evaluated by using Martin’s method is 25.7 cal/mol/K, slightly larger than the Whitesides’ correction in reducing the overestimated entropy.…”

Section: Computational Detailssupporting

confidence: 69%

Hydroboration Reduction of CO₂ Catalyzed by a Doubly Reduced Arylborane: DFT Insight into Double Active-Site and CO₂ Self-Promoting Single Active-Site Mechanisms and Counterion Effects

Zhang,

Lei,

Cao

2023

ACS Catal.

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Hydroboration reduction of CO 2 by HBpin catalyzed by ambiphilic boron centers, a doubly reduced 9,10-dimethyl-9,10-dihydro-9,10diboraanthracene [DBA-Me 2 ] 2− (A0) and its metal salts ( M A0) reported by Wagner, M. et al. (Angew. Chem., Int. Ed. 2018, 57, 16491−16495), has been explored by density functional theory (DFT) calculations. Unexpectedly, the cycloadduct (A1 a ) from the barrier-free activation of CO 2 and bridging across the two B atoms of A0 may serve as a highly active catalyst to boost the CO 2 hydroboration reduction through a single active-site mechanism. The catalytic hydroboration of CO 2 by dianion A0 and its metal salts M n -[DBA-Me 2 ] (n = 2 for M = Li + , Na + , K + ; and n = 1 for M = Mg 2+ , Ca 2+ ) follows the double active-site mechanism, where the diboron site acts as the active center. Generally, the CO 2 hydroboration reduction by HBpin may take place through three independent and cascade subcycles, leading to primary HCOOBpin, secondary HCHO, and reduction product CH 3 OBpin, respectively. Counter cations and THF solvent molecules remarkably influence the activation of HBpin and H 2 by A0, but the relative energetics of the overall hydroboration process mediated by A1 a is less changed. The present results show that the doubly reduced arylborane and its CO 2 adduct, as well as their metal salts are quite promising for the hydroboration reduction of CO 2 .

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Section: Computational Detailssupporting

confidence: 69%

Hydroboration Reduction of CO₂ Catalyzed by a Doubly Reduced Arylborane: DFT Insight into Double Active-Site and CO₂ Self-Promoting Single Active-Site Mechanisms and Counterion Effects

Zhang,

Lei,

Cao

2023

ACS Catal.

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“…Pu and Lei et al carried out theoretical calculations (using DFT method) to investigate further the exact mechanism of the selective hydroboration of α,β-unsaturated esters. [62] Santos et al reported a novel protocol for phophine catalyzed hydroboration of alkynoic esters and amides. [63] This highly chemoselective protocol exclusively provided the transhydroboration product (104) (Scheme 19a) catalyzed by nBu 3 P. The most plausible mechanism was proposed based on theoretical and experimental outcomes (Scheme 19b).…”

Section: Hydroboration Of Carboxylic Esters and Amidesmentioning

confidence: 99%

“…Pu and Lei et al. carried out theoretical calculations (using DFT method) to investigate further the exact mechanism of the selective hydroboration of α,β‐unsaturated esters [62] …”

Section: Metal‐free Catalytic Hydroborationmentioning

confidence: 99%

Metal‐Free Catalytic Hydroboration of Unsaturated Compounds: A Greener Strategy for the Synthesis of Organoboranes

Das

Panda

2022

ChemCatChem

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This review discusses the immense progress made over recent years in metal‐free catalytic hydroboration. Reactions with several unsaturated functional groups, such as alkynes, alkenes, carbonyl compounds, carbon dioxide, carbodiimides, imines, allenes, pyridines, carboxylic acid derivatives etc., have been explored. Although there are significant developments in hydroboration reactions using metal‐based catalysts, metal‐free catalytic strategies are more desirable from a sustainability perspective. Considerable effort has been made by various research groups on metal‐free catalysts in the hydroboration of unsaturated compounds. Lewis acid, Brønsted acid, Lewis acid‐base pairs, and frustrated Lewis pairs were involved as metal‐free sources to catalyze hydroboration reactions in a sustainable manner. Detailed mechanisms of the catalytic pathways of metal‐free hydroboration are also discussed in this review. This discussion will provide an overview of the extent of work carried out as well as indicate scope for future research.

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Synthesis, Structure, and Chemical Properties of 1,3,2-Benzoxazaphospholenes

Klimashevskaya,

Arsenyeva,

Cherkasov

et al. 2023

Russ J Gen Chem

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A theoretical study of the hydroboration of α,β-unsaturated carbonyl compounds catalyzed by a metal-free complex and subsequent C–C coupling with acetonitrile

Abstract: Herein density functional theory (DFT) method was employed to explore the reaction mechanism of selective hydroboration of α,β-unsaturated carbonyl compounds catalyzed by the metal-free complex, 1,3,2-diazaphospholene (DAP). The whole reaction...

Cited by 3 publications

References 58 publications

Hydroboration Reduction of CO₂ Catalyzed by a Doubly Reduced Arylborane: DFT Insight into Double Active-Site and CO₂ Self-Promoting Single Active-Site Mechanisms and Counterion Effects

Hydroboration Reduction of CO₂ Catalyzed by a Doubly Reduced Arylborane: DFT Insight into Double Active-Site and CO₂ Self-Promoting Single Active-Site Mechanisms and Counterion Effects

Metal‐Free Catalytic Hydroboration of Unsaturated Compounds: A Greener Strategy for the Synthesis of Organoboranes

Synthesis, Structure, and Chemical Properties of 1,3,2-Benzoxazaphospholenes

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A theoretical study of the hydroboration of α,β-unsaturated carbonyl compounds catalyzed by a metal-free complex and subsequent C–C coupling with acetonitrile

Abstract: Herein density functional theory (DFT) method was employed to explore the reaction mechanism of selective hydroboration of α,β-unsaturated carbonyl compounds catalyzed by the metal-free complex, 1,3,2-diazaphospholene (DAP). The whole reaction...

Cited by 3 publications

References 58 publications

Hydroboration Reduction of CO2 Catalyzed by a Doubly Reduced Arylborane: DFT Insight into Double Active-Site and CO2 Self-Promoting Single Active-Site Mechanisms and Counterion Effects

Hydroboration Reduction of CO2 Catalyzed by a Doubly Reduced Arylborane: DFT Insight into Double Active-Site and CO2 Self-Promoting Single Active-Site Mechanisms and Counterion Effects

Metal‐Free Catalytic Hydroboration of Unsaturated Compounds: A Greener Strategy for the Synthesis of Organoboranes

Synthesis, Structure, and Chemical Properties of 1,3,2-Benzoxazaphospholenes

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Product

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Hydroboration Reduction of CO₂ Catalyzed by a Doubly Reduced Arylborane: DFT Insight into Double Active-Site and CO₂ Self-Promoting Single Active-Site Mechanisms and Counterion Effects

Hydroboration Reduction of CO₂ Catalyzed by a Doubly Reduced Arylborane: DFT Insight into Double Active-Site and CO₂ Self-Promoting Single Active-Site Mechanisms and Counterion Effects