<i>C</i>-Methylenation of anilines and indoles with CO<sub>2</sub> and hydrosilane using a pentanuclear zinc complex catalyst

Takaishi, Kazuto; Kosugi, Hiroyasu; Nishimura, Ritsuki; Yamada, Yuya; Ema, Tadashi

doi:10.1039/d1cc03675k

Cited by 19 publications

(7 citation statements)

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“…Although several methods for one-pot C-H/C-C bond formation with CO 2 have been reported, 8,9 this type of deoxygenative CO 2 conversion at 30-40 °C is unprecedented. [10][11][12] This catalytic system with BPh 3 and PhSiH 3 is a useful synthetic tool for the deoxygenative CO 2 conversions and concomitant C-C bond formation.…”

Section: Introductionmentioning

confidence: 99%

Deoxygenative CO₂ conversions with triphenylborane and phenylsilane in the presence of secondary amines or nitrogen-containing aromatics

et al. 2022

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Section: Introductionmentioning

confidence: 99%

Deoxygenative CO₂ conversions with triphenylborane and phenylsilane in the presence of secondary amines or nitrogen-containing aromatics

et al. 2022

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“…[50] Next, Ema and Takaishi group accomplished the one-step selective C-methylenation of anilines and indoles catalyzed by 0.5 mol% of macrocyclic pentanuclear Zn(II) complex [Zn 5 L 3 (OAc)(O)]OH using carbon dioxide and phenylsilane under a solvent free condition (Scheme 27). [51]…”

Section: C-methylation Of (Hetero)arenes With Comentioning

confidence: 99%

Recent Trends in Upgrading of CO₂ as a C1 Reactant in N‐ and C‐Methylation Reactions

et al. 2022

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Carbon dioxide (CO 2 ) capture and conversion from renewable resources have recently emerged as a viable alternative to the synthesis of core chemicals. Despite the fact that CO 2 fixation is limited due to its thermodynamic stability and kinetic inertness, researchers are becoming increasingly interested in developing novel routes with the use of CO 2 in synthetic organic chemistry, and the pace of advancements in this field is accelerating. In particular, the development of benign N-and C-methylation reactions employing CO 2 as a C1 synthon instead of conventional methylation reagents would enable the release of lower amounts of waste leading to more sustainable chemical industry. This review presents recent new strategies for the chemical transformation of CO 2 and its incorporation into Nor C-based nucleophiles to provide access to the respective methylamines and methylated (hetero)arenes. Finally, existing limitations in NÀ H, and CÀ H bond activation techniques and future prospects are also discussed. We believe these methodologies will provide a handy reference to the chemists for synthesizing a vast range of methylated molecules in shorter steps by utilizing CO 2 as an advantageous single-carbon source.

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“…In sharp contrast, B(C 6 F 5 ) 3 showed little or no activity under otherwise the same conditions. Although several methods for successive C−H/C−C bond formation with CO 2 have been reported, [8,9] the above deoxygenative CO 2 conversions at 30–40 °C are quite unique [10–12] . In fact, other catalysts reported so far usually require much higher temperature to achieve the N‐methylation of amines with CO 2 and hydrosilane.…”

Section: Introductionmentioning

confidence: 99%

“…Although several methods for successive CÀ H/CÀ C bond formation with CO 2 have been reported, [8,9] the above deoxygenative CO 2 conversions at 30-40 °C are quite unique. [10][11][12] In fact, other catalysts reported so far usually require much higher temperature to achieve the N-methylation of amines with CO 2 and hydrosilane. Therefore, the origin of the high catalytic activity of this catalytic system composed of BPh 3 and PhSiH 3 is quite interesting and worthy of investigation.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of BPh₃‐Catalyzed N‐Methylation of Amines with CO₂ and Phenylsilane: Cooperative Activation of Hydrosilane

Ratanasak

Murata

Adachi

et al. 2022

Chemistry A European J

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BPh 3 catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1methylindoles in the presence of CO 2 and PhSiH 3 ; these reactions proceed at 30-40 °C under solvent-free conditions. In contrast, B(C 6 F 5 ) 3 shows little or no activity. 11 B NMR spectra suggested the generation of [HBPh 3 ] À . The detailed mechanism of the BPh 3 -catalyzed N-methylation of N-methylaniline (1) with CO 2 and PhSiH 3 was studied by using DFT calculations. BPh 3 promotes the conversion of two substrates (N-methylaniline and CO 2 ) into a zwitterionic carbamate to give three-component species. The carbamate and BPh 3 act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH 3 to generate [HBPh 3 ] À , which is used to produce key CO 2 -derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1. DFT calculations also suggested other mechanisms involving water for the generation of [HBPh 3 ] À species.

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C-Methylenation of anilines and indoles with CO₂ and hydrosilane using a pentanuclear zinc complex catalyst

Abstract: The one-step C-methylenation of anilines and indoles with CO2 and phenylsilane was catalyzed by a pentanuclear ZnII complex to give diarylmethanes via geminal C−H and C−C bond formation. It is...

Cited by 19 publications

References 59 publications

Deoxygenative CO₂ conversions with triphenylborane and phenylsilane in the presence of secondary amines or nitrogen-containing aromatics

Deoxygenative CO₂ conversions with triphenylborane and phenylsilane in the presence of secondary amines or nitrogen-containing aromatics

Recent Trends in Upgrading of CO₂ as a C1 Reactant in N‐ and C‐Methylation Reactions

Mechanism of BPh₃‐Catalyzed N‐Methylation of Amines with CO₂ and Phenylsilane: Cooperative Activation of Hydrosilane

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C-Methylenation of anilines and indoles with CO2 and hydrosilane using a pentanuclear zinc complex catalyst

Abstract: The one-step C-methylenation of anilines and indoles with CO2 and phenylsilane was catalyzed by a pentanuclear ZnII complex to give diarylmethanes via geminal C−H and C−C bond formation. It is...

Cited by 19 publications

References 59 publications

Deoxygenative CO2 conversions with triphenylborane and phenylsilane in the presence of secondary amines or nitrogen-containing aromatics

Deoxygenative CO2 conversions with triphenylborane and phenylsilane in the presence of secondary amines or nitrogen-containing aromatics

Recent Trends in Upgrading of CO2 as a C1 Reactant in N‐ and C‐Methylation Reactions

Mechanism of BPh3‐Catalyzed N‐Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane

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Resources

About

C-Methylenation of anilines and indoles with CO₂ and hydrosilane using a pentanuclear zinc complex catalyst

Deoxygenative CO₂ conversions with triphenylborane and phenylsilane in the presence of secondary amines or nitrogen-containing aromatics

Deoxygenative CO₂ conversions with triphenylborane and phenylsilane in the presence of secondary amines or nitrogen-containing aromatics

Recent Trends in Upgrading of CO₂ as a C1 Reactant in N‐ and C‐Methylation Reactions

Mechanism of BPh₃‐Catalyzed N‐Methylation of Amines with CO₂ and Phenylsilane: Cooperative Activation of Hydrosilane