Iron-Catalyzed Coupling of Alkenes and Enones: Sakurai–Michael-type Conjugate Addition of Catalytic Allyliron Nucleophiles DOI Creative Commons

Sarah G. Scrivener,

Yidong Wang, Yiming Wang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(9), P. 1420 - 1424

Published: Feb. 27, 2023

The iron-catalyzed coupling of alkenes and enones through allylic C(sp3)–H functionalization is reported. This redox-neutral process employs a cyclopentadienyliron(II) dicarbonyl catalyst simple alkene substrates to generate catalytic allyliron intermediates for 1,4-addition chalcones other conjugated enones. use 2,4,6-collidine as the base combination triisopropylsilyl triflate LiNTf2 Lewis acids was found facilitate this transformation under mild, functional group-tolerant conditions. Both electronically unactivated well allylbenzene derivatives could be employed pronucleophilic partners, range bearing varied substituents.

Language: Английский

Efficient Synthesis of Sulfur-Stereogenic Sulfoximines via Ru(II)-Catalyzed Enantioselective C–H Functionalization Enabled by Chiral Carboxylic Acid DOI
Tao Zhou, Pu‐Fan Qian, Jun-Yi Li

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(18), P. 6810 - 6816

Published: April 28, 2021

Ru(II)-catalyzed enantioselective C-H functionalization involving an enantiodetermining cleavage step remains undeveloped. Here we describe a activation/annulation of sulfoximines with α-carbonyl sulfoxonium ylides using novel class chiral binaphthyl monocarboxylic acids as ligands, which can be easily and modularly prepared from 1,1'-binaphthyl-2,2'-dicarboxylic acid. A broad range sulfur-stereogenic were in high yields excellent enantioselectivities (up to 99% yield ee) via desymmetrization, kinetic resolution, parallel resolution. Furthermore, the resolution products transformed sulfoxides key intermediates for kinase inhibitors.

Language: Английский

Citations

165

Chiral Carboxylic Acid Assisted Enantioselective C–H Activation with Achiral CpxMIII (M = Co, Rh, Ir) Catalysts DOI
Tatsuhiko Yoshino, Shigeki Matsunaga

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(11), P. 6455 - 6466

Published: May 17, 2021

Enantioselective C–H functionalization is a powerful tool for synthesizing chiral molecules. In the past few years, combination of high-valent group 9 metals with achiral Cpx ligands and carboxylic acids (CCA) has emerged as promising catalytic system to enable selective cleavage enantiotopic bonds. This Perspective summarizes background, catalyst design, applied reactions in detail, followed by discussion future directions.

Language: Английский

Citations

120

Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions DOI
Chen‐Xu Liu,

Si‐Yong Yin,

Fangnuo Zhao

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 10079 - 10134

Published: Aug. 1, 2023

This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during last two decades. Parallel to rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity reactions. In recent years, Rh-catalyzed have been significantly many respects, including catalyst design, reaction development, mechanistic investigation, application synthesis complex functional molecules. presents an explicit outline catalysts ligands, mechanism, scope coupling reagents, applications.

Language: Английский

Citations

120

Transition-metal-catalyzed C–H bond alkylation using olefins: recent advances and mechanistic aspects DOI
Debasish Mandal,

Sumali Roychowdhury,

Jyoti Prasad Biswas

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(17), P. 7358 - 7426

Published: Jan. 1, 2022

Transition metal catalysis has contributed immensely to C-C bond formation reactions over the last few decades, and alkylation is no exception. The superiority of such methodologies traditional evident from minimal reaction steps, shorter times, atom economy while also allowing control regio- stereo-selectivity. In particular, hydrocarbonation alkenes grabbed increased attention due its fundamental ability effectively selectively synthesise a wide range industrially pharmaceutically relevant moieties. This review attempts provide scientific viewpoint systematic analysis recent developments in transition-metal-catalyzed various C-H bonds using simple activated olefins. key features mechanistic studies involved these transformations are described briefly.

Language: Английский

Citations

83

Cobalt(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective Synthesis of Benzothiadiazine‐1‐oxides via C−H Activation DOI
Yuuki Hirata,

Daichi Sekine,

Yoshimi Kato

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(28)

Published: May 2, 2022

Abstract Among sulfoximine derivatives containing a chiral sulfur center, benzothiadiazine‐1‐oxides are important for applications in medicinal chemistry. Here, we report that the combination of an achiral cobalt(III) catalyst and pseudo‐ C 2 ‐symmetric H 8 ‐binaphthyl carboxylic acid enables asymmetric synthesis from sulfoximines dioxazolones via enantioselective C−H bond cleavage. With optimized protocol, with several functional groups can be accessed high enantioselectivity.

Language: Английский

Citations

74

Electrooxidative Rhodium(III)/Chiral Carboxylic Acid‐Catalyzed Enantioselective C−H Annulation of Sulfoximines with Alkynes DOI
Gang Zhou, Tao Zhou,

Ao‐Lian Jiang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Jan. 30, 2024

Abstract The combination of achiral Cp*Rh(III) with chiral carboxylic acids (CCAs) represents an efficient catalytic system in transition metal‐catalyzed enantioselective C−H activation. However, this hybrid catalysis is limited to redox‐neutral activation reactions and the adopt oxidative remains elusive pose a significant challenge. Herein, we describe development electrochemical Cp*Rh(III)‐catalyzed annulation sulfoximines alkynes enabled by acid (CCA) operationally friendly undivided cell at room temperature. A broad range enantioenriched 1,2‐benzothiazines are obtained high yields excellent enantioselectivities (up 99 % yield 98 : 2 er). practicality method demonstrated scale‐up reaction batch reactor external circulation. crucial intermediate isolated, characterized, transformed, providing rational support for Rh(III)/Rh(I) electrocatalytic cycle.

Language: Английский

Citations

20

Facile synthesis of axially chiral styrene-type carboxylic acids via palladium-catalyzed asymmetric C–H activation DOI Creative Commons
Chi Yang,

Tian-Rui Wu,

Yan Li

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(10), P. 3726 - 3732

Published: Jan. 1, 2021

Palladium-catalyzed asymmetric C–H functionalization to yield axially chiral styrene-type carboxylic acids is described, in which axial chirality and sterically hindered group were incorporated one-step.

Language: Английский

Citations

70

Synthesis of Chiral Spirolactams via Sequential C−H Olefination/Asymmetric [4+1] Spirocyclization under a Simple CoII/Chiral Spiro Phosphoric Acid Binary System DOI
Wen‐Kui Yuan, Bing‐Feng Shi

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(43), P. 23187 - 23192

Published: Aug. 26, 2021

Abstract An unprecedented enantioselective synthesis of spiro‐γ‐lactams via a sequential C−H olefination/asymmetric [4+1] spirocyclization under simple Co II /chiral spiro phosphoric acid (SPA) binary system is reported. A range biologically important are obtained with high levels enantioselectivity (up to 98 % ee ). The concise, asymmetric an aldose reductase inhibitor was successfully achieved. Notably, contrast previous reports that relied on the use cyclopentadienyl or its derivatives (achiral Cp*, Cp tBu , chiral x ) ligated III complexes requiring tedious steps prepare, cheap and commercially available cobalt(II) acetate tetrahydrate used as efficient precatalyst.

Language: Английский

Citations

70

Development of Pseudo-C2-symmetric Chiral Binaphthyl Monocarboxylic Acids for Enantioselective C(sp3)–H Functionalization Reactions under Rh(III) Catalysis DOI

Yoshimi Kato,

Luqing Lin, M. Kojima

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(7), P. 4271 - 4277

Published: March 22, 2021

Enantioselective C(sp3)–H functionalization reactions using high-valent group 9 metal catalysts with cyclopentadienyl ligands have been achieved by the introduction of appropriate chiral carboxylic acids. However, diversity acids, as well that applicable substrate structures remains limited. Herein, we report pseudo-C2-symmetric tunable acids a binaphthyl backbone and their application to enantioselective amidation 2-alkylpyridines related heteroaromatic substrates. The fixed cyclic structure pseudo-C2-symmetry developed would reduce conformational flexibility ambiguity. combination an optimal acid sterically hindered rhodium catalyst (Cp*tBuRhIII) exhibited high enantioselectivity (up 96:4 er).

Language: Английский

Citations

61

Ruthenium(II)/Imidazolidine Carboxylic Acid‐Catalyzed C−H Alkylation for Central and Axial Double Enantio‐Induction DOI Creative Commons
Yanjun Li,

Yan‐Cheng Liou,

João C. A. Oliveira

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(47)

Published: Sept. 15, 2022

Enantioselective C-H activation has surfaced as a transformative toolbox for the efficient assembly of chiral molecules. However, despite major advances in rhodium and palladium catalysis, ruthenium(II)-catalyzed enantioselective thus far largely proven elusive. In contrast, we herein report on highly regio-, diastereo- alkylation. The key to success was represented by identification novel C2-symmetric imidazolidine carboxylic acids (CICAs), which are easily accessible one-pot fashion, effective ligands. This ruthenium/CICA system enabled installation central axial chirality, featured excellent branched linear ratios with generally >20 : 1 dr up 98 2 er. Mechanistic studies experiment computation were carried out understand catalyst mode action.

Language: Английский

Citations

56