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 Dynamic Kinetic Asymmetric Arylation of Secondary Phosphine-Boranes for the Synthesis of P(III)-Stereogenic Centers DOI
Xue Wang, Xiao Jin,

Lei Ge

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 14, 2025

Transition-metal-catalyzed asymmetric C-P(III) bond formation is a direct method for the construction of P(III)-stereogenic centers; however, achieving high enantioselectivity remains challenge. Herein, an unprecedented Cu-catalyzed dynamic kinetic resolution secondary phosphine-boranes was successfully developed. This C-P(BH3) coupling reaction provided and highly enantioselective synthesis centers, enabling chiral medium-sized benzophosphine-boranes (7-10-membered cycles). A mechanism involving unusual rapid racemization has been proposed.

Language: Английский

Citations

0
Stereogenic P(V) Synthesis via Catalytic Continuous Substitutions DOI

Gaoliang Zheng,

Yuchen Zhang, Jingming Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 9, 2025

Phosphorus(V) stereocenters that are fully substituted by heteroatoms play important roles in bioactive molecules and organocatalysts. Existing methods to achieve such motifs rely almost entirely on resolution or diastereocontrol, prefunctionalized substrates usually required generate specific P(V) stereocenters. In contrast, related catalytic rare, no generally applicable method is described. Here, we report a modular strategy access broad variety of stereogenic-at-phosphorus skeletons, including ProTide analogs, alkoxylphosphoramidates, phosphates, phosphorothioates, phosphonamidates, through designed enantioselective continuous substitutions simple precursors. The nucleophilic substitution sequence readily determined the stereoconfiguration products. Concise synthesis analogs drug demonstrated practical value protocol. Experimental computational studies unveiled unique π-π stacking effect chalcogen bonding interaction between catalyst substrate as origin stereoselectivity.

Language: Английский

Citations

0
Nickel-Catalyzed Asymmetric Synthesis of Ambiphilic Secondary Phosphine Oxides DOI

Wei-Han Wang,

Siyu Zhang, Yu-Xiang Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 16, 2025

The synthesis of ambiphilic compounds, which possess both strong nucleophilic and electrophilic functional groups, presents a significant challenge due to their propensity self-react, forming oligomers or polymers. We have successfully achieved the nickel-catalyzed asymmetric P-stereogenic alkenyl secondary phosphine oxides from tailored primary oxide by leveraging controversial stability reactivity. This method demonstrates remarkable tolerance toward wide range unactivated alkynes, including those derived natural products medicinally relevant molecules, thus providing universal synthon for phosphines with high enantioselectivity regioselectivity. product exhibits interesting orthogonal reactivities nucleophiles electrophiles can be easily converted variety compounds.

Language: Английский

Citations

0
Copper-catalyzed aryl ortho-C–H thiolation of aldehydes via a transient directing group strategy DOI Creative Commons

Ming-Shun Mei,

Dong Kee Yi, Fanyi Meng

et al.

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The Cu-catalyzed C–H thiolation reaction of aromatic aldehydes has been developed via a transient directing group strategy.

Language: Английский

Citations

0
Pd-catalyzed enantioselective and regioselective asymmetric hydrophosphorylation and hydrophosphinylation of enynes DOI

Yanxin Jiang,

Kwai Wun Cheng,

Zhiping Yang

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: unknown, P. 110231 - 110231

Published: July 1, 2024

Language: Английский

Citations

3
Copper‐Catalyzed C(sp2)−C(sp2) Bond Formation via Single C(sp2)−H Activation DOI

Himanshu V. Parmar,

Yash J. Adodariya,

Unnati P. Patel

et al.

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(2)

Published: Jan. 9, 2024

Abstract This review provides a comprehensive overview and evaluation of the studies conducted over past 15 years into copper catalyzed reactions for C(sp 2 )−C(sp ) bond formation via )−H activation. The investigations encompass wide array starting materials substrates. range substrates studied has been broadened to C−H activation aryls, heteroaryls, alkenyl groups. Furthermore, in some cases only catalytic amounts salts were required drive challenging functionalization, indicating promising avenue future research.

Language: Английский

Citations

2
Synthesis of P‐Stereogenic Compounds by Transition Metal‐Catalyzed Asymmetric Transformation of H−P(O) Compounds: Progress, Challenges, and Prospects DOI

Kang Ding,

Bo Su

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 27(4)

Published: Dec. 5, 2023

Abstract The synthesis of P‐stereogenic phosphorus compounds has gained considerable attention due to their wide applications across many research fields. Among the available strategies, transition metal‐catalyzed asymmetric transformation pentavalent phosphoryl (H−P(O)) precursors is particularly appealing. This approach involves a direct C−P bond‐forming process, rendering it straightforward, and employs readily available, bench‐stable H−P(O) reagents that are compatible with various metal catalysts. Recent years have witnessed significant progress in this field, primary focus on cross‐couplings hydrophosphorylations. Concept article provides brief summary recent progress, highlights existing challenges, discusses future directions exciting area.

Language: Английский

Citations

6
Enantioselective Synthesis of Indole‐Derivated Axially Chiral Frameworks via CpXRh(III)‐Catalyzed Domino Cyclization/C3‐Arylation of 2‐Alkynylanilines with 1‐Diazonaphthoquinones DOI
Junwei Ye,

Qingwei Song,

Dongping Pan

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(5), P. 1064 - 1069

Published: Jan. 13, 2024

Abstract We report herein a chiral Cp X Rh(III)‐catalyzed domino cyclization/C 3 ‐arylation process using 2‐alkynylanilines and 1‐diazonaphthoquinones as viable substrates, delivering indole‐based derivatives endowed with axial chirality. The method features high enantioselectivity, broad substrate scope, robust functional group tolerance. Subsequent functionalization of the synthesized scaffolds underlines practicality this approach in design indole‐derivated axially frameworks, demonstrating its substantial promise synthetic medicinal chemistry applications.

Language: Английский

Citations

1
Solvent‐Controlled Enantiodivergent Construction of P(V)‐Stereogenic Molecules via Palladium‐Catalyzed Annulation of Prochiral N‐Aryl Phosphonamides with Aromatic Iodides DOI

Qingyu Tian,

Jin Ge,

Yaopeng Liu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(41)

Published: July 9, 2024

Abstract In this work, we describe an efficient and modular method for enantiodivergent accessing P(V)‐stereogenic molecules by utilizing the catalytic atroposelective Catellani‐type C−H arylation/desymmetric intramolecular N ‐arylation cascade reaction. The enantioselectivity of protocol was proved to be tuned polarity solvent, thus providing a wide range both chiral enantiomers in moderate good yields with excellent enantiomeric excesses. Noteworthy is that strategy developed herein represents unprecedented example solvent‐dictated inversion compounds.

Language: Английский

Citations

1
Synthesis of P-Stereogenic Phosphinamides via Nickel-Catalyzed Kinetic Resolution of H-Phosphinamides by Alkenylation and Arylation DOI
Cheng Xu, Jing Zhao, Yu Zheng

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(41), P. 8662 - 8667

Published: Oct. 4, 2024

A nickel-catalyzed enantioselective cross-coupling for the synthesis of P-stereogenic phosphinamides has been developed. The asymmetric alkenylation and arylation racemic H-phosphinamides using alkenyl aryl bromides resulted in formation N-phosphinyl compounds with good yields high enantioselectivities. This method tolerates a variety functional groups, its applications are explored through scale-up reactions product transformations.

Language: Английский

Citations

1