Asymmetric synthesis of allylic compoundsviahydrofunctionalisation and difunctionalisation of dienes, allenes, and alkynes

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(7), P. 2060 - 2118

Published: Jan. 1, 2020

This review article provides an overview of progress in asymmetric synthesis allylic compoundsviahydrofunctionalisation and difunctionalisation dienes, allenes, alkynes.

Language: Английский

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P-Chiral Phosphines Enabled by Palladium/Xiao-Phos-Catalyzed Asymmetric P–C Cross-Coupling of Secondary Phosphine Oxides and Aryl Bromides

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(51), P. 20556 - 20564

Published: Dec. 2, 2019

The development of transition-metal-catalyzed methods for the synthesis P-chiral phosphine derivatives poses a considerable challenge. Herein, we present direct Pd/Xiao-Phos-catalyzed cross-coupling reaction easily accessible secondary oxides and aryl bromides, which provides rapid access to oxides. proceeds efficiently with wide array partners deliver various tertiary in up 96% yield 97% ee. Moreover, DiPAMP ligand its analogues was also realized, demonstrates suitable pathway switching branched chain DiPAMP.

Language: Английский

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1,2,3-Triazole and Its Analogues: New Surrogates for Diazo Compounds

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(15), P. 13108 - 13205

Published: July 19, 2022

Readily accessible and shelf-stable 1,2,3-triazole its analogues such as pyridotriazole, triazoloindole, benzotriazole, thiadiazole exist in equilibrium with their ring-opened isomers, viz., diazo compounds. These isomers could be trapped by various metal catalysts (e.g., Rh, Pd, Cu, Co, Ag, etc.) to generate the corresponding carbenoids extrusion of nitrogen. As a consequence, these unique N-heterocycles facilitate access realm N-containing complex structural motifs biological importance through denitrogenative transformations transannulations, insertions, ylide formation, rearrangements trapping diverse range coupling partners alkenes, alkynes, nitriles, carbo/heterocycles, X-H/C-X bonds, etc.). Hence, suitably substituted triazole derivatives have emerged efficient surrogates compounds for generation reactive during past decades. In this comprehensive review, we aim discuss detail remarkable advancement synthesis synthetic applications.

Language: Английский

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Pd-Catalyzed Enantioselective Heck Reaction of Aryl Triflates and Alkynes

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(49), P. 19246 - 19251

Published: Nov. 20, 2019

The first palladium-catalyzed asymmetric Heck reaction between aryl triflates and alkynes to give trisubstituted allenes with high er under mild conditions is described. key the success discovery fine-tuning of different N-substituents Xu-Phos, which ensure enantioselectivity reactivity. Synthetic transformation chiral chirality transfer was also demonstrated.

Language: Английский

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Synthesis of Heterocycles through Denitrogenative Cyclization of Triazoles and Benzotriazoles

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(52), P. 11931 - 11945

Published: May 19, 2020

Abstract During the past few decades, there has been considerable growth in development of denitrogenative reactions triazole skeletons to construct valuable cyclic compounds, particularly heterocycles. Despite inherent difficulty ring‐opening derivatives, many novel and efficient approaches have arisen this area mainly with use transition metal (such as rhodium, palladium, silver, copper) catalysis, photolysis, or free radical mediated reactions. Generally, these procedures begin 1,2,3‐triazoles benzotriazoles followed by N 2 extrusion subsequent diverse transformations, which enable rapid synthesis various heterocycles a single step. To avoid overlap other related reviews, minireview covers recent advances cyclization since 2016 2012.

Language: Английский

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Design and Synthesis of TY‐Phos and Application in Palladium‐Catalyzed Enantioselective Fluoroarylation ofgem‐Difluoroalkenes

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(51), P. 22957 - 22962

Published: Sept. 25, 2020

Abstract The first example of highly enantioselective fluoroarylation gem‐difluoroalkenes with aryl halides is presented by using a new chiral sulfinamide phosphine ( Sadphos ) type ligand TY‐Phos . N‐Me‐ can be easily synthesized on gram scale from readily available starting materials in three steps. Salient features this work including materials, good yields, high enantioselectivities as well broad substrate scope make approach very practical and attractive. Notably, the asymmetric synthesis an analogue biologically active molecule also reported.

Language: Английский

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Axially Chiral Biaryl Monophosphine Oxides Enabled by Palladium/WJ-Phos-Catalyzed Asymmetric Suzuki–Miyaura Cross-coupling

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(2), P. 1548 - 1554

Published: Jan. 3, 2020

A highly enantioselective palladium/WJ-Phos-catalyzed Suzuki–Miyaura coupling reaction for efficient construction of axially chiral biaryl monophosphine oxides was developed. series were obtained in good yields and with high enantioselectivities. The practicability this validated the straightforward synthesis ligand demonstrated by a 100-g-scale synthesis. Moreover, various functionalizations product make it as platform molecule other phosphines.

Language: Английский

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Asymmetric Dearomatization of Indole by Palladium/PC‐Phos‐Catalyzed Dynamic Kinetic Transformation

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(49), P. 21991 - 21996

Published: Sept. 2, 2020

Abstract A palladium‐catalyzed intermolecular dynamic kinetic asymmetric dearomatization of 3‐arylindoles with internal alkynes was developed the use achiral Xantphos and chiral sulfinamide phosphine ligand ( PC‐Phos ) as co‐ligands. This method could deliver various spiro[indene‐1,3′‐indole] compounds in good yields (up to 95 % yield) up 98 ee . The salient features transformation include readily available substrates, ease scale‐up versatile functionalization products. mechanistic experiments gave some insights on active intermediates.

Language: Английский

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Transition‐Metal‐Catalyzed Denitrogenative Annulation to Access High‐Valued N‐Heterocycles

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(2)

Published: Oct. 13, 2022

Abstract Over the past few years, development of efficient methods to construct high‐valued N ‐heterocyclic molecules have received massive attention owing their extensive application in areas medicinal chemistry, drug discovery, natural product synthesis and so on. To access those N‐heterocycles, many been developed. In this context, transition‐metal‐catalyzed denitrogenative annulation 1,2,3‐triazoles 1,2,3,4‐tetrazoles has appeared as a powerful synthetic tool because it offers step‐ atom‐economical route for preparation nitrogen‐rich molecules. Compared with various 1,2,3‐triazole frameworks, 1,2,3,4‐tetrazole remains more challenging due inertness tetrazole moiety. This Review summarizes significant achievements made field including some pioneering examples area research. We anticipate that reaction will find broad applications pharmaceutical industry, discovery other fields chemistry.

Language: Английский

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Recent advances in Pd-catalyzed asymmetric cyclization reactions

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(2), P. 883 - 971

Published: Dec. 18, 2023

This review aims to collect advancements in enantioselective palladium-catalyzed cyclization reactions over the past eleven years, and it is organized into thirteen sections depending on different types of transformations involved.

Language: Английский

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