Highlighting multicomponent reactions as an efficient and facile alternative route in the chemical synthesis of organic-based molecules: a tremendous growth in the past 5 years DOI Creative Commons
Reagan L. Mohlala, Thompho Jason Rashamuse,

E. Mabel Coyanis

et al.

Frontiers in Chemistry, Journal Year: 2024, Volume and Issue: 12

Published: Sept. 18, 2024

Since Strecker’s discovery of multicomponent reactions (MCRs) in 1850, the strategy applying an MCR approach has been use for over a century. Due to their ability quickly develop molecular diversity and structural complexity interest, MCRs are considered efficient organic synthesis. Although such as Ugi, Passerini, Biginelli, Hantzsch widely studied, this review emphasizes significance selective elegantly produce compounds potential medicinal chemistry industrial material science applications, well sustainable methods. During synthesis, provide advantages atom economy, recyclable catalysts, moderate conditions, preventing waste, avoiding solvent use. also reduce number sequential multiple one step.

Language: Английский

Cobalt/Salox‐Catalyzed Enantioselective C−H Functionalization of Arylphosphinamides DOI
Qi‐Jun Yao, Jiahao Chen, Hong Song

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(25)

Published: April 6, 2022

Previous methods on CoIII -catalyzed asymmetric C-H activation rely the use of tailor-made cyclopentadienyl-ligated complexes, which require lengthy steps for preparation. Herein, we report an unprecedented enantioselective functionalization enabled by a simple cobalt/salicyloxazoline (Salox) catalysis. The chiral Salox ligands can be easily prepared in one step from salicylonitrile and amino alcohols. A broad range P-stereogenic compounds were synthesized high yields with excellent enantioselectivities (45 examples, up to 99 % yield >99 ee). isolation characterization several intermediates provided insights into generation active catalytic cobalt species, action Salox, mode stereocontrol.

Language: Английский

Citations

95
Atroposelective isoquinolinone synthesis through cobalt-catalysed C–H activation and annulation DOI

Xiao‐Ju Si,

Dandan Yang,

Meng-Chan Sun

et al.

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(9), P. 709 - 718

Published: July 18, 2022

Language: Английский

Citations

79
Single‐Step Synthesis of Atropisomers with Vicinal C−C and C−N Diaxes by Cobalt‐Catalyzed Atroposelective C−H Annulation DOI
Bingjie Wang,

Guo‐Xiong Xu,

Zong‐Wei Huang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(39)

Published: Aug. 2, 2022

The atroposelective synthesis of atropisomers with vicinal diaxes remains rare and challenging, due to the steric influence between two axes their unique topology. Herein, we disclose a single-step construction C-C C-N chiral by cyclopentadiene (Cp)-free cobalt-catalyzed intramolecular C-H annulation, providing desired diaxial structures decent stereocontrols both (up >99 % ee 70 : 1 dr). optically pure products bearing fluorophores show circular polarized luminescence (CPL) properties, being candidate materials for potential CPL applications. Atropisomerization experiments density function theory (DFT) calculations are conducted study rotational barriers rotation pathways diaxes.

Language: Английский

Citations

77
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

73
Cobalt-catalyzed atroposelective C−H activation/annulation to access N−N axially chiral frameworks DOI Creative Commons
Tong Li, Linlin Shi,

Xinhai Wang

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Aug. 29, 2023

The N-N atropisomer, as an important and intriguing chiral system, was widely present in natural products, pharmaceutical lead compounds, advanced material skeletons. anisotropic structural characteristics caused by its special axial rotation have always been one of the challenges that chemists strive to overcome. Herein, we report efficient method for enantioselective synthesis axially frameworks via a cobalt-catalyzed atroposelective C-H activation/annulation process. reaction proceeds under mild conditions using Co(OAc)2·4H2O catalyst with salicyl-oxazoline (Salox) ligand O2 oxidant, affording variety products high yields enantioselectivities. This protocol provides approach facile construction atropisomers further expands range derivatives. Additionally, electrocatalysis, desired were also successfully achieved good excellent efficiencies

Language: Английский

Citations

52
Cobalt-Catalyzed Enantioselective C–H Annulation with Alkenes DOI
Dandan Yang, Xian Zhang, Xinghua Wang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 4250 - 4260

Published: March 13, 2023

Herein, we disclose an efficient cobalt-catalyzed enantioselective C–H activation and annulation of benzamides with alkenes. This transformation is facilitated via the commercially available cobalt(II) catalyst in presence easily prepared chiral salicyl-oxazoline (Salox) ligand, which provides facile access to (R) or (S) enantiomers dihydroisoquinolone derivatives. It noticeable that reaction proceeded efficiently within extremely short time from 10 30 min under mild conditions. A broad range alkenes bear various functional substituents have been shown good compatibility deliver targeted products high yields enantioselectivities (51 examples, up 98% yield 99% ee). The gram scale experiment removal directing group further demonstrate practicability this protocol potential industrial applications. Density theory calculations elucidate mechanism, spin-state change olefin insertion step accelerates subsequent C–N reductive elimination, identified as stereo-determining step. AIM analysis indicates π interactions are vital for controlling switching stereoselectivity.

Language: Английский

Citations

45
Cobalt/Salox‐Catalyzed Enantioselective Dehydrogenative C−H Alkoxylation and Amination DOI
Jiahao Chen,

Ming‐Ya Teng,

Fan‐Rui Huang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(38)

Published: Aug. 2, 2022

The past decade has witnessed a rapid progress in asymmetric C-H activation. However, the enantioselective alkoxylation and amination with alcohols free amines remains elusive. Herein, we disclose first dehydrogenative enabled by simple cobalt/salicyloxazoline (Salox) catalysis. use of cheap readily available cobalt(II) salts as catalysts Saloxs chiral ligands provides an efficient method to access P-stereogenic compounds excellent enantioselectivities (up >99 % ee). practicality this protocol is demonstrated gram-scale preparation further derivatizations resulting phosphinamides, which offering flexible alternative mono- diphosphine ligands. Preliminary mechanistic studies on reaction suggest that cobalt(III/IV/II) catalytic cycle might be involved.

Language: Английский

Citations

62
Enantioselective C−H functionalization reactions enabled by cobalt catalysis DOI Creative Commons
Yang Zheng, Chao Zheng, Qing Gu

et al.

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(11), P. 2965 - 2985

Published: Sept. 16, 2022

Language: Английский

Citations

44
Synthesis of P-stereogenic cyclicphosphinic amidesviaelectrochemically enabled cobalt-catalyzed enantioselective C–H annulation DOI
Tao Liu,

Wangqin Zhang,

Chao Xu

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(9), P. 3606 - 3614

Published: Jan. 1, 2023

We describe a cobalta-electro-catalyzed enantioselective C–H annulation of arylphosphinamides with alkynes for P-stereogenic compounds via desymmetrization and kinetic resolution processes.

Language: Английский

Citations

40
O-Allylhydroxyamine: A Bifunctional Olefin for Construction of Axially and Centrally Chiral Amino Alcohols via Asymmetric Carboamidation DOI

Ruijie Mi,

Zhiying Ding,

Songjie Yu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(14), P. 8150 - 8162

Published: April 4, 2023

Difunctionalization of olefins offers an attractive approach to access complex chiral structures. Reported herein is the design N-protected O-allylhydroxyamines as bifunctional that undergo catalytic asymmetric 1,2-carboamidation with three classes (hetero)arenes afford amino alcohols via C-H activation. The C═C bond in O-allylhydroxyamine activated by intramolecular electrophilic amidating moiety well a migrating directing group. carboamidation reaction pattern depends on nature (hetero)arene reagent. Simple achiral reacted give centrally β-amino excellent enantioselectivity. employment axially prochiral or racemic heteroarenes afforded both axial and central chirality enantio- diastereoselectivity. In case heteroarenes, coupling follows kinetic resolution s-factor up >600. A nitrene-based mechanism has been suggested based experimental studies, unique mode induction diastereoselectivity proposed. Applications alcohol products have demonstrated.

Language: Английский

Citations

38