Computational study of Cu-catalyzed 1,2-hydrocarboxylation of 1,3-dienes with CO<sub>2</sub>: Pauli repulsion-controlled regioselectivity of Cu–Bpin additions

Hu, Yanlei; Hu, Lingfei; Gao, Han; Lv, Xiangying; Wu, Yanbo; Lü, Gang

doi:10.1039/d2qo00236a

Cited by 11 publications

(3 citation statements)

References 81 publications

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“…12 1,3-Dienes are readily accessible chemicals and direct C–H bond allylation with 1,3-dienes, as an atom economical process, has been well studied. 13 However, the regioselective C–H bond allylation of phenols with 1,3-dienes has seen far less exploration, with only two examples reported to date. In a seminal study reported by Li and coworkers in 2019, ortho -selectivity was obtained by B(C 6 F 5 ) 3 catalysis (Fig.…”

Section: Introductionmentioning

confidence: 99%

Nickel/Brønsted acid dual-catalyzed regioselective C–H bond allylation of phenols with 1,3-dienes

2022

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Section: Introductionmentioning

confidence: 99%

Nickel/Brønsted acid dual-catalyzed regioselective C–H bond allylation of phenols with 1,3-dienes

2022

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“…The transmetalation of borone ester and copper salt produced allylic copper species, which reacted with CO 2 to deliver the corresponding acid products. Very recently, the mechanism and origin of regioselectivity of this reaction were computationally investigated by Lu and co‐workers [40] . As a carboxylation reagent, CO 2 in the reaction also facilitated to generate the key allyl copper intermediate.…”

Section: Copper‐catalyzed Carboxylation Of C−c Double Bondsmentioning

confidence: 99%

“…Very recently, the mechanism and origin of regioselectivity of this reaction were computationally investigated by Lu and co-workers. [40] As a carboxylation reagent, CO 2 in the reaction also facilitated to generate the key allyl copper intermediate.…”

Section: Carboxylation Of Dienesmentioning

confidence: 99%

Recent Advances in Copper‐Catalyzed Carboxylation Reactions with CO₂

Song

Chen

2022

Asian J Org Chem

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As an ideal one-carbon synthon, CO 2 has been successfully utilized in diverse carboxylation reactions to construct a series of value-added products. Among various transition-metal catalysts, the inexpensive copper complexes exhibit unique catalytic activity in carboxylation reactions. This review summarizes the recent developments in copper-catalyzed carboxylation reactions with CO 2 , the contents of which are divided into five parts based on the type of the substrates or products: organic halides and their surrogates, CÀ C double bonds, CÀ C triple bonds, CÀ H bonds and the synthesis of heterocycles.

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Mechanism and Origins of Diastereo‐ and Regioselectivities of Palladium‐Catalyzed Remote Diborylative Cyclization of Dienes via Chain‐Walking Strategy

Kong

Zhang

Wang

et al. 2022

Chemistry An Asian Journal

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Density functional theory calculations have been performed to investigate the palladium‐catalyzed remote diborylative cyclization of dienes. The computations reveal that the reaction proceeds through a rarely explored Pd(II)/Pd(IV) catalytic cycle, and the formal σ‐bond metathesis between the alkylpalladium intermediate and B2pin2 occurs via the pathway of the B−B oxidative addition/C−B reductive elimination involving the high‐valent Pd(IV) species. The diastereoselectivity is determined by the migratory insertion into the Pd−C bond, which is mainly due to the combination of the torsional strain effect, steric repulsion and C−H—O hydrogen‐bonding interaction. The steric hindrance around the reacting carbon group in the C−B reductive elimination turns out to be a key factor to provide the driving force of the chain walking of the Pd center to the terminal primary carbon position, enabling the experimentally observed remote regioselectivity.

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Computational study of Cu-catalyzed 1,2-hydrocarboxylation of 1,3-dienes with CO₂: Pauli repulsion-controlled regioselectivity of Cu–Bpin additions

Abstract: The mechanism and origin of regioselectivity of Cu-catalyzed 1,2-hydrocarboxylation of 1,3-dienes with CO2 were computationally investigated. The results show that CO2 not only acts as a carboxylation reagent, but also...

Cited by 11 publications

References 81 publications

Nickel/Brønsted acid dual-catalyzed regioselective C–H bond allylation of phenols with 1,3-dienes

Nickel/Brønsted acid dual-catalyzed regioselective C–H bond allylation of phenols with 1,3-dienes

Recent Advances in Copper‐Catalyzed Carboxylation Reactions with CO₂

Mechanism and Origins of Diastereo‐ and Regioselectivities of Palladium‐Catalyzed Remote Diborylative Cyclization of Dienes via Chain‐Walking Strategy

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Computational study of Cu-catalyzed 1,2-hydrocarboxylation of 1,3-dienes with CO2: Pauli repulsion-controlled regioselectivity of Cu–Bpin additions

Abstract: The mechanism and origin of regioselectivity of Cu-catalyzed 1,2-hydrocarboxylation of 1,3-dienes with CO2 were computationally investigated. The results show that CO2 not only acts as a carboxylation reagent, but also...

Cited by 11 publications

References 81 publications

Nickel/Brønsted acid dual-catalyzed regioselective C–H bond allylation of phenols with 1,3-dienes

Nickel/Brønsted acid dual-catalyzed regioselective C–H bond allylation of phenols with 1,3-dienes

Recent Advances in Copper‐Catalyzed Carboxylation Reactions with CO2

Mechanism and Origins of Diastereo‐ and Regioselectivities of Palladium‐Catalyzed Remote Diborylative Cyclization of Dienes via Chain‐Walking Strategy

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Computational study of Cu-catalyzed 1,2-hydrocarboxylation of 1,3-dienes with CO₂: Pauli repulsion-controlled regioselectivity of Cu–Bpin additions

Recent Advances in Copper‐Catalyzed Carboxylation Reactions with CO₂