Synthesis of Enamines, Aldehydes, and Nitriles from CO2: Scope of the One-Pot Strategy via Formamides DOI

Koichi Nakaoka,

Chao Guo,

Yuta Saiki

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 88(21), P. 15444 - 15451

Published: Sept. 13, 2022

Tetrabutylammonium acetate (TBAA) and Cu(OAc)2 worked as a binary catalytic system for the solvent-free N-formylation of amines with CO2 PhSiH3. This catalysis making C-H C-N bonds was coupled C-C bond-forming reactions to achieve one-pot synthesis enamines, aldehydes, nitriles. The X-ray crystal structure Cu(OAc)2-TBAA complex also revealed.

Language: Английский

Facile approach to multifunctionalized 5-alkylidene-3-pyrrolin-2-ones via regioselective oxidative cyclization of 2,4-pentanediones with primary amines and sodium sulfinates DOI
Donghan Liu,

Xihang Lu,

Qiaohe Zhang

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(15), P. 4078 - 4084

Published: Jan. 1, 2022

Highly functionalized 5-alkylidene-3-pyrrolin-2-ones were efficiently synthesized via a four-component cascade cyclization/sulfonylation reaction between readily available 2,4-pentanediones, primary amines and sodium sulfinates under mild conditions.

Language: Английский

Citations

17
Four-electron reduction of CO2: from formaldehyde and acetal synthesis to complex transformations DOI Creative Commons
Sarah Desmons, Julien Bonin, Marc Robert

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(37), P. 15023 - 15086

Published: Jan. 1, 2024

The expansive and dynamic field of the CO2 Reduction Reaction (CO2RR) seeks to harness as a sustainable carbon source or energy carrier. While significant progress has been made in two, six, eight-electron reductions CO2, four-electron reduction remains understudied. This review fills this gap, comprehensively exploring into formaldehyde (HCHO) acetal-type compounds (EOCH2OE, with E = [Si], [B], [Zr], [U], [Y], [Nb], [Ta] -R) using various CO2RR systems. These encompass (photo)electro-, bio-, thermal processes diverse reductants. Formaldehyde, versatile C1 product, is challenging synthesize isolate from CO2RR. also discusses acetal compounds, emphasizing their significance pathways distinct reactivity. Providing an overview state reduction, highlights achievements, challenges, potential produced - acetals sources for valuable product synthesis, including chiral compounds.

Language: Английский

Citations

3
Deoxygenative CO2 conversions with triphenylborane and phenylsilane in the presence of secondary amines or nitrogen-containing aromatics DOI

Takumi Murata,

Mahoko Hiyoshi,

Shinsuke Maekawa

et al.

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(6), P. 2385 - 2390

Published: Jan. 1, 2022

BPh 3 catalyzed the N -methylation of secondary amines and C -methylenation , -dimethylanilines or 1-methylindoles in presence CO 2 PhSiH without solvent at 30–40 °C, a cascade reaction from 1-methyl-2-oxindole also proceeded.

Language: Английский

Citations

15
Controllable methylenation with ethylene glycol as the methylene source: bridging enaminones and synthesis of tetrahydropyrimidines DOI
Yulei Zhao, Huimin Wang,

Xin Kang

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(21), P. 5935 - 5941

Published: Jan. 1, 2022

Controllable methylenation using renewable ethylene glycol as the methylene source has been developed for introduction of one or two building blocks.

Language: Английский

Citations

15
C-Methylenation of anilines and indoles with CO2 and hydrosilane using a pentanuclear zinc complex catalyst DOI
Kazuto Takaishi,

Hiroyasu Kosugi,

Ritsuki Nishimura

et al.

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(65), P. 8083 - 8086

Published: Jan. 1, 2021

The one-step C-methylenation of arenes with CO2 and phenylsilane was catalyzed by a pentanuclear ZnII complex to give diarylmethanes via C–H C–C bond formation.

Language: Английский

Citations

20
PhB(OH)2-Promoted Electrochemical Sulfuration–Formyloxylation of Styrenes and Selectfluor-Mediated Oxidation–Olefination DOI
Yulei Zhao,

Xuqiang Guo,

Shuai Li

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(23), P. 9140 - 9145

Published: Nov. 16, 2021

We report a PhB(OH)2-promoted electrochemical sulfuration-formyloxylation reaction of styrenes employing commercially available thiophenols/thiols as thiolating agents. Specifically, metal catalysts and external chemical oxidants are not needed in the for formation β-formyloxy sulfides, these sulfides can be further converted to (E)-vinyl sulfones via Selectfluor-mediated oxidation-olefination. Notably, on basis this oxidation strategy, β-hydroxy sulfide, sulfoxide, sulfone, sulfoxide also easily prepared.

Language: Английский

Citations

18
Construction of 1,4-Dihydropyridines: The Evolution of C4 Source DOI
Siyu Song, Yongchao Wang, Fuchao Yu

et al.

Topics in Current Chemistry, Journal Year: 2023, Volume and Issue: 381(5)

Published: Sept. 25, 2023

Language: Английский

Citations

7
Mechanism of BPh3‐Catalyzed N‐Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane DOI
Manussada Ratanasak,

Takumi Murata,

Taishin Adachi

et al.

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(58)

Published: Aug. 30, 2022

BPh3 catalyzes the N-methylation of secondary amines and C-methylenation (methylene-bridge formation between aromatic rings) N,N-dimethylanilines or 1-methylindoles in presence CO2 PhSiH3 ; these reactions proceed at 30-40 °C under solvent-free conditions. In contrast, B(C6 F5 )3 shows little no activity. 11 B NMR spectra suggested generation [HBPh3 ]- . The detailed mechanism -catalyzed N-methylaniline (1) with was studied by using DFT calculations. promotes conversion two substrates (N-methylaniline ) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N+ CO2- ⋅⋅⋅BPh3 ]. act as nucleophile Lewis acid, respectively, for activation generate , which is used produce key -derived species, such silyl formate bis(silyl)acetal, essential 1. calculations also other mechanisms involving water species.

Language: Английский

Citations

11
One-Pot Synthesis of Dihydropyrans via CO2 Reduction and Domino Knoevenagel/oxa-Diels–Alder Reactions DOI
Kazuto Takaishi,

Ritsuki Nishimura,

Yuha Toda

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(9), P. 1370 - 1374

Published: Feb. 24, 2023

Catalytic CO2 reduction with phenylsilane under solvent-free conditions was linked the one-pot synthesis of 3,4-dihydropyrans from β-dicarbonyl compounds and styrenes. The includes three processes: (1) bis(silyl)acetal formation a domino reaction (2) Knoevenagel condensation (3) inverse-electron-demand oxa-Diels-Alder reaction. first process catalyzed by pentanuclear ZnII complex (0.07 mol %) to generate bis(silyl)acetals, which were hydrolyzed into formaldehyde be used in second step.

Language: Английский

Citations

6
N-Methylation of Aniline Derivatives with CO2 and Phenylsilane Catalyzed by Lanthanum Hydridotriarylborate Complexes bearing a Nitrogen Tridentate Ligand DOI
Koichi Shinohara, Hayato Tsurugi, Kazushi Mashima

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(14), P. 8220 - 8228

Published: June 24, 2022

A lanthanum amide complex, La(L)[N(SiHMe2)2](thf) (L = N,N″-bis(pentafluorophenyl)diethylenetriamine dianion, 1a), upon activation with B(3,4,5-F2C6H2)3 (2a), showed excellent catalytic activity for N-methylation of N-alkylaniline derivatives CO2 in the presence PhSiH3. catalytically active hydridotriarylborate [La(L)(thf)2][HB(3,4,5-F3C6H2)3] (5aa), was generated via hydride abstraction from Si–H moiety 1a by moderate Lewis acid 2a THF. DFT studies hydrosilylation step clarified following multiple noncovalent interactions as key factors locating HB(3,4,5-F2C6H2)3 anion and B(3,4,5-F3C6H2)3 near center transition states reduction Si–O bond formation: (1) π–π interaction between electron-deficient C6F5 ring on ligand L 3,4,5-F3C6H2 HB(3,4,5-F3C6H2)3 (2) C–H···F hydrogen bonds ortho-C–H fluorine atoms L.

Language: Английский

Citations

9