Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(18)

Опубликована: Фев. 21, 2024

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 S

Язык: Английский

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Metal-catalyzed Markovnikov-type selective hydrofunctionalization of terminal alkynes

Chemical Society Reviews, Год журнала: 2024, Номер 53(14), С. 7566 - 7589

Опубликована: Янв. 1, 2024

Metal-catalyzed highly Markovnikov-type selective hydrofunctionalization of terminal alkynes provides a straightforward and atom-economical route to access 1,1-disubstituted alkenes, which have wide range applications in organic synthesis. However, the transformations are challenging due electronic steric effects during addition process. With development metal-catalyzed synthesis, different metal catalysts been developed solve this challenge, especially for platinum group catalysts. In perspective, we review homogeneous according classified element types as well reaction mechanisms. Future avenues investigation also presented help expand exciting field.

Язык: Английский

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Ni-catalyzed propargylic substitution reaction: A general and versatile tool to assemble axially chiral phosphorus-containing allenes

Chem Catalysis, Год журнала: 2024, Номер 4(3), С. 100903 - 100903

Опубликована: Фев. 1, 2024

Язык: Английский

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Enantio‐ and Regioselective Cascade Hydroboration of Methylenecyclopropanes for Facile Access to Chiral 1,3‐ and 1,4‐Bis(boronates)

Advanced Science, Год журнала: 2024, Номер 11(21)

Опубликована: Март 13, 2024

Abstract Chiral 1, n‐bis(boronate) plays a crucial role in organic synthesis and medicinal chemistry. However, their catalytic asymmetric has long posed challenge terms of operability accessibility from readily available substrates. The recent discovery the C═C bond formation through β‐C elimination methylenecyclopropanes (MCP) provided an exciting opportunity to enhance molecular complexity. In this study, catalyzed cascade hydroboration MCP is developed. By employing different ligands, various homoallylic boronate intermediate are obtained ring opening process. Subsequently, with HBpin or B 2 pin resulted enantioenriched chiral 1,3‐ 1,4‐bis(boronates) high yields, accompanied by excellent chemo‐ enantioselectivities. selective transformation these two distinct C─B bonds also demonstrated application potential synthesis.

Язык: Английский

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Enantioselective Zn-Catalyzed Hydrophosphinylation of Nitrones: An Efficient Approach for Constructing Chiral α-Hydroxyamino-Phosphine Oxides

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Although enantioselective hydrofunctionalizations of nitrones are established for synthesis various types chiral hydroxylamines, the asymmetric catalytic hydrophosphinylation remains highly challenging. Herein, an efficient of...

Язык: Английский

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