Stereodivergent synthesis of α-fluoro α-azaaryl γ-butyrolactones via cooperative copper and iridium catalysis DOI Creative Commons

Kui Tian,

Xin Chang,

Lu Xiao

et al.

Fundamental Research, Journal Year: 2022, Volume and Issue: 4(1), P. 77 - 85

Published: July 30, 2022

The development of stereodivergent synthetic methods to access all four stereoisomers biologically important α-fluoro γ-butyrolactones containing vicinal stereocenters is great importance and poses a formidable challenge owing ring strain steric hindrance. Herein, novel asymmetric [3+2] annulation α-azaaryl acetates with vinylethylene carbonate was successfully developed through Cu/Ir-catalyzed cascade allylic alkylation/lactonization, affording variety enantioenriched bearing stereogenic centers high reaction efficiency excellent levels both stereoselectivity regioselectivity (up 98% yield, generally >20:1 dr >99% ee). Notably, these pharmaceutically valuable molecules could be accessed individually

Language: Английский

Advances in Palladium‐Catalyzed Decarboxylative Cycloadditions of Cyclic Carbonates, Carbamates and Lactones DOI
Yong You, Qun Li, Yanping Zhang

et al.

ChemCatChem, Journal Year: 2022, Volume and Issue: 14(9)

Published: Jan. 31, 2022

Abstract Palladium‐catalyzed decarboxylative cycloadditions have emerged as highly effective methods for constructing structurally diverse carbo‐ and heterocycles because of the formation at least two carbon‐carbon or carbon‐heteroatom bonds in a single step. It is great interest to chemists that this type cycloaddition reactions possesses some special advantages such high reactivity, exclusive regioselectivity, good functional group compatibility. Based on these qualities, palladium‐catalyzed present strong ability synthetic chemistry been flourished especially last five years. In review, achievements involving cyclic carbonates, carbamates, lactones accessing oxacyclo‐, azacyclo‐ carbocyclic compounds are addressed. Mechanistic insights applications toward synthesis natural products discussed. The challenges opportunities field also outlined.

Language: Английский

Citations

70
Recent advances in annulation reactions based on zwitterionic π-allyl palladium and propargyl palladium complexes DOI
Ben Niu, Yin Wei, Min Shi

et al.

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(13), P. 3475 - 3501

Published: Jan. 1, 2021

Carbocyclic and heterocyclic compounds could be constructed through the palladium-catalyzed annulation reactions of zwitterionic π-allyl palladium or propargyl complexes with unsaturated electrophiles.

Language: Английский

Citations

76
Recent advances in Pd-catalyzed asymmetric cyclization reactions DOI
Bing Xu,

Quanpu Wang,

Chao Fang

et al.

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

Citations

41
Temperature-Controlled Divergent Asymmetric Synthesis of Indole-Based Medium-Sized Heterocycles through Palladium Catalysis DOI
Qing‐Zhu Li,

Yi-Long Guan,

Qianwei Huang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(2), P. 1164 - 1172

Published: Jan. 4, 2023

The divergent construction of chiral medium-sized rings is an essential but challenging task in organic synthesis. Herein, we report a temperature-controlled catalytic system for the divergent, enantioselective synthesis different types starting from same substrate set. Enabled by planar bisphosphine ligand, palladium-catalyzed (5 + 4) and formal 2) annulations cyclic aza-dienes vinylethylene carbonates proceeded smoothly to afford broad spectrum indole-based heterocycles excellent yields with outstanding enantioselectivities. Those products could be further diversified through various functional group transformations. Moreover, mechanistic studies, including control experiments DFT calculations, shed light on understanding observed regio- enantioselectivities n) cyclization.

Language: Английский

Citations

33
Fungicide-inspired precursors of π-allylpalladium intermediates for palladium-catalyzed decarboxylative cycloadditions DOI Creative Commons
Kuan Li,

Shuo Zhen,

Wang Wang

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(11), P. 3024 - 3029

Published: Jan. 1, 2023

Inspired by a fungicide, we designed 5-vinyloxazolidine-2,4-diones as new precursors of π-allylpalladium zwitterionic intermediates and developed palladium-catalyzed asymmetric (5 + 3) cycloaddition with azomethine imines (3 2) 1,1-dicyanoalkenes. Both reactions proceeded smoothly under mild reaction conditions to produce various chiral heterocyclic compounds in high yields excellent enantioselectivities. These results revealed that were type suitable precursor for palladium catalysis will find extensive applications Pd-catalyzed such allylic alkylation.

Language: Английский

Citations

27
Recent advances in copper-catalyzed decarboxylative reactions of propargylic cyclic carbonates/carbamates DOI
Yong You, Yanping Zhang, Zhen‐Hua Wang

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(49), P. 7483 - 7505

Published: Jan. 1, 2023

Copper-catalyzed decarboxylative reactions are powerful strategies for the construction of widely available skeletons such as allenes, ethynyl-containing heterocycles, and quaternary carbon centers.

Language: Английский

Citations

23
Palladium-Catalyzed Ligand-Directed Divergent Decarboxylative Cycloadditions of Vinyloxazolidine-2,4-diones with 1,3,5-Triazinanes DOI
Zhen‐Hua Wang, Xiaohui Fu, Qun Li

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(8), P. 1589 - 1594

Published: Feb. 22, 2024

This study demonstrates a highly efficient regiodivergent ligand-controlled palladium-catalyzed cycloaddition reaction of vinyloxazolidine-2,4-diones with 1,3,5-triazinanes. In the presence diphosphine ligand, proceeds via (5+2) pathway to afford 1,3-diazepin-4-ones in excellent yields, while using monophosphine smoothly (3+2) give imidazolidin-4-ones good yields.

Language: Английский

Citations

9
Modular Synthesis of Medium-Sized Fluorinated and Nonfluorinated Heterocyclic Lactones by Sequential CN-Bond-Cleaving Ring Expansion under Pd Catalysis DOI

Hiroto Uno,

Koki Kawai,

Motoo Shiro

et al.

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(23), P. 14117 - 14126

Published: Nov. 18, 2020

Fluoro-functionalized heterocycles and medium-sized are both attractive skeletons in medicinal chemistry. However, the construction of fluoro-functionalized remains unexplored. Their synthesis represents a formidable challenge due to unfavorable entropic enthalpic factors that arise from rings unexpected properties induced by fluorinated groups. Here, we describe an efficient method for preparation highly functionalized gem-difluoromethylene N-heterocyclic lactones with 9- 11-membered sequential CN-bond-cleaving ring-expansion process using difluoro-oxindoles, various zwitterion precursors, Pd catalyst. This CN-cleaving expansion was extended synthesize nonfluorinated, α-keto-lactone moiety isatin derivatives. Additionally, monofluorinated nonfluorinated oxindoles were transformed into corresponding heterocyclic this protocol. The key transformation is cleavage unreactive amide CN bond, which smartly activated incorporation two neighboring electron-withdrawing groups assisted nucleophilic attack Pd-coordinated zwitterion. site-selective functionalization series products demonstrated show their synthetic utility. Mechanistic details cleavage/expansion proposed based on liquid chromatography–mass spectrometry (LC–MS) analyses.

Language: Английский

Citations

56
Dual Cobalt/Organophotoredox Catalysis for Diastereo- and Regioselective 1,2-Difunctionalization of 1,3-Diene Surrogates Creating Quaternary Carbon Centers DOI

Sijing Xue,

Àlex Cristòfol, Bart Limburg

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(6), P. 3651 - 3659

Published: March 7, 2022

The synthesis of compounds having quaternary carbon centers through a catalytic stereo- and regioselective difunctionalization 2-substituted 1,3-dienes remains elusive. Here, we present dual Co/photoredox-catalyzed cascade approach that addresses this challenge using modular vinyl cyclic carbonates functioning as masked 2-aryl-1,3-diene surrogates. latter species are conveniently prepared in situ converted into nucleophilic Co(allyl) intermediates intercepted by aldehydes to afford homoallylic alcohols with ample scope reaction partners. developed protocol marks significant step forward the use structurally versatile their 1,2-hydroalkylation 1,2-dicarbofunctionalization.

Language: Английский

Citations

35
Enantio‐, Diastereo‐ and Regioselective Synthesis of Chiral Cyclic and Acyclic gem‐Difluoromethylenes by Palladium‐Catalyzed [4+2] Cycloaddition DOI

Hiroto Uno,

Koki Kawai,

Taichi Araki

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(24)

Published: March 28, 2022

gem-Difluoromethylene moieties are attractive in medicinal chemistry due to their ability mimic other more ubiquitous functional groups. Thus, effective asymmetric methods for construction highly desirable, especially the industrial production of chiral drugs. Using a Pd-catalyzed [4+2] cycloaddition between substituted-2-alkylidenetrimethylene carbonates and gem-difluoroalkyl ketones, we were able easily access 1,3-dioxanes that contain tetrasubstituted difluoroalkyl stereogenic center cyclic acyclic skeletons. A novel phosphoramidite ligand, which contains bulky 1,1-dinaphthylmethanamino moiety, was developed provide products high yield with excellent enantio-, diastereo-, regioselectivity. Strikingly, gem-difluoro substitution pattern promotes reaction, pentafluoroethylketone, an α,α-difluorinated β-ketoester, β-ketosulfone suitable substrates this method.

Language: Английский

Citations

31