Thiourea-Assisted Chiral Bicyclic Imidazole Organocatalysts: Design, Synthesis, and Application in Asymmetric Acylative Desymmetrization of Bisphenols for the Construction of P-Stereocenters DOI
Chenglong Hu, Xuyang Tang,

Baochi Zhang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 16300 - 16306

Published: Dec. 6, 2023

Thiourea-assisted chiral bicyclic imidazole organocatalysts were designed, synthesized, and successfully applied in the asymmetric acylative desymmetrization of P-prochiral bisphenols. Under mild conditions, P-stereogenic products obtained high yields (up to 99% yield) with enantioselectivities ee). Most importantly, reaction could also achieve satisfactory results under 1 mol % catalyst loadings. Mechanistic studies showed that synergistic effect including covalent activation acyl group by nucleophilic noncovalent H-bonding π-interaction between substrate was crucial for efficient construction P-stereocenters.

Language: Английский

Palladium-catalyzed asymmetric hydrophosphination of internal alkynes: Atroposelective access to phosphine-functionalized olefins DOI Creative Commons

Danqing Ji,

Jierui Jing,

Yi Wang

et al.

Chem, Journal Year: 2022, Volume and Issue: 8(12), P. 3346 - 3362

Published: Sept. 23, 2022

Language: Английский

Citations

79
P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis DOI
Tsuneo Imamoto

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(14), P. 8657 - 8739

Published: July 2, 2024

Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality and P-stereogenic ligands. Most reported belong to former class. Privileged ones such as BINAP DuPhos frequently employed wide range catalytic transformations. In contrast, latter class has remained small family many years mainly because their synthetic difficulty. The late 1990s saw emergence novel with superior enantioinduction ability Rh-catalyzed hydrogenation reactions. Since then, numerous have been synthesized used This Review summarizes thus far, including stereochemical electronic properties that afford high excellent enantioselectivities. Examples reactions use this described together applications construction key intermediates natural products therapeutic agents. literature covered dates back 1968 up until December 2023, centering on studies published later years.

Language: Английский

Citations

43
Asymmetric C–H Activation for the Synthesis of P- and Axially Chiral Biaryl Phosphine Oxides by an Achiral Cp*Ir Catalyst with Chiral Carboxylic Amide DOI

Chao-Wei Zhang,

Hu XianQi,

Yuan‐Hao Dai

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 12(1), P. 193 - 199

Published: Dec. 14, 2021

The catalytic synthesis of P- and axially chiral biaryl phosphine oxides was realized via the Cp*Ir-catalyzed asymmetric C–H coupling tertiary substituted with diarylacetylenes. carboxylic amides were used to control stereoselectivity in activation, enabling construction up 96% ee. Transformation products into trivalent ligands has also been demonstrated.

Language: Английский

Citations

58
Ni-catalyzed asymmetric hydrophosphinylation of conjugated enynes and mechanistic studies DOI Creative Commons
Yaqian Zhang,

Xue-Yu Han,

Yue Wu

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(14), P. 4095 - 4102

Published: Jan. 1, 2022

The catalytic asymmetric synthesis of

Language: Английский

Citations

55
Ni-Catalyzed Enantioselective Benzylation of Secondary Phosphine Oxide DOI

Wen-Qiang Cai,

Wei Qi, Qing‐Wei Zhang

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(5), P. 1258 - 1262

Published: Feb. 2, 2022

A nickel-catalyzed benzylic substitution of secondary phosphine oxide was described, affording the dialkylated P-stereogenic tertiary oxides with high to excellent enantioselectivities. The reaction performed under mild conditions commercially available benzyl chlorides and bench stable oxides, exhibiting broad functional group tolerance. It represented a practical example for preparation compounds.

Language: Английский

Citations

43
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
Bulky P-stereogenic ligands. A success story in asymmetric catalysis DOI Creative Commons
Pep Rojo, Antoni Riéra, Xavier Verdaguer

et al.

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 489, P. 215192 - 215192

Published: May 9, 2023

Since the development of BisP* ligand by Imamoto, P-stereogenic phosphines bearing a bulky tert-butyl group and smaller alkyl have demonstrated extraordinary proficiency in wide range asymmetric processes. Over time, this class ligands has brought about introduction more rigid backbones, three-hindered quadrant concept, substitution adamantyl. The methyl fragment also been introduced phosphino-oxazoline-type ligands, chemists industrial sector contributed to evolution reporting first successful Buchwald-type monophosphines for coupling reactions. present review covers synthesis applications that developed since advent late 1990s, with special emphasis on successfully applied catalysis.

Language: Английский

Citations

37
Synthesis of P‐Stereogenic Phosphine Oxides via Nickel‐Catalyzed Asymmetric Cross‐Coupling of Secondary Phosphine Oxides with Alkenyl and Aryl Bromides DOI Open Access
Chuanyong Wang,

Xiaobo Hu,

Cheng Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(15)

Published: Feb. 14, 2023

Abstract A general and mild nickel‐catalyzed enantioselective C(sp 2 )−P cross‐coupling for synthesizing P‐stereogenic phosphine oxides has been developed. The asymmetric alkenylation/arylation of racemic secondary with alkenyl/aryl bromides generated high yields enantioselectivities. Various functional groups were tolerated, the applications this method demonstrated through late‐stage functionalization product transformations.

Language: Английский

Citations

35
Copper‐Catalyzed Dynamic Kinetic Asymmetric P−C Coupling of Secondary Phosphine Oxides and Aryl Iodides DOI

Jie Kang,

Kang Ding,

Si‐Mu Ren

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(25)

Published: April 14, 2023

Abstract Transition‐metal‐catalyzed enantioselective P−C cross‐coupling of secondary phosphine oxides (SPOs) is an attractive method for synthesizing P ‐stereogenic phosphorus compounds, but the development such a dynamic kinetic asymmetric process remains considerable challenge. Here we report unprecedented highly intermolecular coupling SPOs and aryl iodides catalyzed by copper complexes ligated finely modified chiral 1,2‐diamine ligand. The reaction tolerates wide range iodides, affording tertiary (TPOs) in high yields with good enantioselectivity (average 89.2 % ee). resulting enantioenriched TPOs were transformed into structurally diverse ‐chiral scaffolds, which are valuable as ligands catalysts synthesis.

Language: Английский

Citations

35
Palladium‐Catalyzed Enantio‐ and Regioselective Ring‐Opening Hydrophosphinylation of Methylenecyclopropanes DOI Creative Commons
Jian Zhou, Ling Meng, Shujuan Lin

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(26)

Published: April 26, 2023

Transition metal-catalyzed hydrofunctionalization of methylenecyclopropanes (MCPs) has presented a considerable challenge due to the difficult manipulation regioselectivity and complicated reaction patterns. Herein, we report straightforward Pd-catalyzed ring-opening hydrophosphinylation MCPs via highly selective C-C bond cleavage. This method allows for rapid efficient access wide range chiral allylic phosphine oxides in good yields high enantioselectivities. Additionally, density functional theory (DFT) calculations were performed elucidate mechanism origin enantioselectivity.

Language: Английский

Citations

33