Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at P(V): Improved Generality, Efficiency and Modularity DOI Creative Commons
Michele Formica, Branislav Ferko, T. R. Marsh

et al.

Published: Dec. 5, 2023

A second generation catalytic two-phase strategy for the enantioselective synthesis of chiral at P(V) compounds is described. This protocol, consisting a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization prochiral, bench stable precursors and subsequent enantiospecific substitution allows divergent access to wide range C-, N-, O- S- substituted containing from handful enantioenriched precursors. new catalyst/leaving group combination allowed far wider substrate scope increased reaction efficiency practicality over previously established protocols. The resulting intermediates could then be converted an even greater distinct classes by displacement remaining leaving as well allowing further diversification downstream. Density functional theory (DFT) calculations were performed pinpoint origin enantioselectivity BIMP-catalyzed desymmetrization, rationalize how superior leads generality in our second-generation system, shed light onto observed retention inversion pathways when performing late-stage SN2@P reactions with Grignard reagents.

Language: Английский

Copper‐Catalyzed Enantioselective Hydrophosphorylation of Unactivated Alkynes DOI

Jie Kang,

Kang Ding,

Si‐Mu Ren

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 5, 2024

Abstract P‐stereogenic phosphorus compounds are essential across various fields, yet their synthesis via enantioselective P−C bond formation remains both challenging and underdeveloped. We report the first copper‐catalyzed hydrophosphorylation of alkynes, facilitated by a newly designed chiral 1,2‐diamine ligand. Unlike previous methods that rely on kinetic resolution with less than 50 % conversion, our approach employs distinct dynamic asymmetric transformation mechanism, achieving complete conversion racemic starting materials. This reaction is compatible broad range aromatic aliphatic terminal producing products high yields (up to 95 %), exclusive cis selectivity, exceptional regio‐ enantioselectivity (>20 : 1 r.r. up 96 ee). The resulting were further transformed into diverse array enantioenriched scaffolds. Preliminary mechanistic studies conducted elucidate details.

Language: Английский

Citations

1
Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity DOI Creative Commons
Michele Formica, Branislav Ferko, T. R. Marsh

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(18)

Published: Feb. 21, 2024

Abstract A broadly improved second generation catalytic two‐phase strategy for the enantioselective synthesis of stereogenic at phosphorus (V) compounds is described. This protocol, consisting a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization prochiral, bench stable P(V) precursors and subsequent enantiospecific substitution allows divergent access to wide range C ‐, N O ‐ S substituted containing from handful enantioenriched intermediates. new ureidopeptide BIMP catalyst/thiaziolidinone leaving group combination allowed far wider substrate scope increased reaction efficiency practicality over previously established protocols. The resulting intermediates could then be transformed into an even greater distinct classes by displacement remaining as well allowing further diversification downstream. Density functional theory (DFT) calculations were performed pinpoint origin enantioselectivity BIMP‐catalyzed desymmetrization, rationalize how superior catalyst/leaving leads generality in our second‐generation system, shed light onto observed stereochemical retention inversion pathways when performing late‐stage 2@P reactions with Grignard reagents.

Language: Английский

Citations

0
Cu-Catalyzed Functionalization of Heterocycles Through C–H Activation DOI

Subarna Pan,

Rajarshi Samanta

Topics in heterocyclic chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Language: Английский

Citations

0
Palladium-Catalyzed Enantioselective Synthesis of P(V)-Stereogenic Compounds via Desymmetric Annulation of Prochiral Phosphinamides and Aryl Iodides DOI

Qingyu Tian,

Jin Ge,

Yaopeng Liu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 27(1), P. 121 - 128

Published: Dec. 30, 2024

The enantioselective synthesis of P(V)-stereogenic compounds has emerged as an interesting research topic primarily due to their significant biological activity and broad application prospects. Herein, we disclose a method for the construction from prochiral phosphinamides aryl iodides via palladium- chiral norbornene-catalyzed desymmetric annulation. were formed with scope excellent enantiomeric excesses. It is noteworthy that synthetic value this procedure was proven by variety transition metal-catalyzed cross-coupling reactions using C–Br bond on product versatile linchpin electrophile.

Language: Английский

Citations

0
Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at P(V): Improved Generality, Efficiency and Modularity DOI Creative Commons
Michele Formica, Branislav Ferko, T. R. Marsh

et al.

Published: Dec. 5, 2023

A second generation catalytic two-phase strategy for the enantioselective synthesis of chiral at P(V) compounds is described. This protocol, consisting a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization prochiral, bench stable precursors and subsequent enantiospecific substitution allows divergent access to wide range C-, N-, O- S- substituted containing from handful enantioenriched precursors. new catalyst/leaving group combination allowed far wider substrate scope increased reaction efficiency practicality over previously established protocols. The resulting intermediates could then be converted an even greater distinct classes by displacement remaining leaving as well allowing further diversification downstream. Density functional theory (DFT) calculations were performed pinpoint origin enantioselectivity BIMP-catalyzed desymmetrization, rationalize how superior leads generality in our second-generation system, shed light onto observed retention inversion pathways when performing late-stage SN2@P reactions with Grignard reagents.

Language: Английский

Citations

1