Ligand-Controlled Cobalt-Catalyzed Regiodivergent Alkyne Hydroalkylation

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(30), P. 13961 - 13972

Published: July 22, 2022

Regiodivergent alkyne hydroalkylation to generate different isomers of an alkene from the same starting material would be beneficial; however, it remains a challenge. Herein, we report ligand-controlled cobalt-catalyzed regiodivergent hydroalkylation. The sensible selection bisoxazoline (L1) and pyridine-oxazoline (L8) ligands led reliable predictable protocols that provided (E)-1,2-disubstituted 1,1-disubstituted alkenes with high E/Z stereoselectivity regioisomeric ratio identical terminal alkyl halide substrates produced trisubstituted in case internal alkynes. This method exhibits broad scope for alkynes wide range activated unactivated halides shows excellent functional group compatibility.

Language: Английский

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Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(85), P. 12669 - 12684

Published: Jan. 1, 2023

Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

Language: Английский

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Photoinduced difunctionalization with bifunctional reagents containing N-heteroaryl moieties

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(6), P. 1688 - 1700

Published: May 10, 2023

Language: Английский

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Site‐selective Hydrogenation/Deuteration of Benzylic Olefins Enabled by Electroreduction Using Water

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(32)

Published: March 27, 2023

We describe an operationally simple and user-friendly protocol that allows the site-selective hydrogenation deuteration of di-, tri- tetrasubstituted benzylic olefins by electroreduction while other groups prone to are present. The radical anionic intermediates react with most inexpensive hydrogen/deuterium source H2 O/D2 O. Our method overcomes many limitations arise from previously reported electroreductive hydrogenations. applicability this reaction is demonstrated a broad substrate scope (>50 examples) focuses on functional group tolerance sites affected metal-catalyzed (alkenes, alkynes, protecting groups).

Language: Английский

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Recent Advances in N-Heterocyclic Carbene Coinage Metal Complexes in A3-Coupling and Carboxylation Reaction

Catalysts, Journal Year: 2023, Volume and Issue: 13(5), P. 811 - 811

Published: April 27, 2023

Owing of their accessibility and wide range reactivities, alkynes make for fascinating building blocks. Either a selective alkyne carbon-carbon triple bond reaction or activation the terminal C-H may be employed to functionalize them. Monocationic coinage metal complexes with d10 electronic configuration are effective catalysts activation. Silver(I) gold(I) N-heterocyclic (NHC) systems emerging as promising in multicomponent reactions; this review paper focuses on A3 (aldehyde-amine-alkyne)-coupling carbon dioxide fixation, furnishing systematic overview scientific advances achieved during last two decades. This study will carefully compare corresponding silver gold processes. The differences routes brought about by catalyst ligand structure investigated an emphasis evaluating benefits provided easily tuneable NHC backbone, terms chemo- stereo-selectivity.

Language: Английский

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Copper‐Catalyzed Regiodivergent Asymmetric Difunctionalization of Terminal Alkynes

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

Published: June 25, 2024

We herein describe the first example of ligand-controlled, copper-catalyzed regiodivergent asymmetric difunctionalization terminal alkynes through a cascade hydroboration and hydroallylation process. The catalytic system, consisting (R)-DTBM-Segphos CuBr, could efficiently achieve 1,1-difunctionalization aryl alkynes, while ligand switching to (S,S)-Ph-BPE result in 1,2-difunctionalization exclusively. In addition, alkyl substituted especially industrially relevant acetylene propyne, were also valid feedstocks for 1,1-difunctionalization. This protocol is characterized by good functional group tolerance, broad scope substrates (>150 examples), mild reaction conditions. showcase value this method late-stage functionalization complicated bioactive molecules simplifying synthetic routes toward key intermediacy natural product (bruguierol A). Mechanistic studies combined with DFT calculations provide insight into mechanism origins ligand-controlled regio- stereoselectivity.

Language: Английский

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Highly selective scalable electrosynthesis of 4-hydroxybenzo[e]-1,2,4-thiadiazine-1,1-dioxides

Cell Reports Physical Science, Journal Year: 2024, Volume and Issue: 5(5), P. 101927 - 101927

Published: April 15, 2024

4H-4-Hydroxybenzo[e]-1,2,4-thiadiazine-1,1-dioxides are based on a widely found structural motif for pharmaceutical applications, having an additional unique exocyclic N–O bond that is not accessible by conventional synthetic routes. Electrochemistry offers sustainable tool the direct synthesis of these heterocyclic structures containing this N-hydroxy modification. Here, we report highly selective 4H-4-hydroxybenzo[e]-1,2,4-thiadiazine-1,1-dioxides reduction available nitro arenes in almost quantitative yields. The electro-synthetic protocol applied to more than 40 diverse examples, highlighting versatility method. Furthermore, technical relevance demonstrated two multi-gram-scale syntheses.

Language: Английский

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Rh(II)/Pd(0) Dual-Catalyzed Regio-Divergent Three-Component Propargylic Substitution

JACS Au, Journal Year: 2023, Volume and Issue: 3(10), P. 2862 - 2872

Published: Sept. 25, 2023

Regio-divergent propargylic substitution to generate functionally diverse products from identical starting materials remains a formidable challenge, probably due the unpredictable regiochemical complexity. In practically, synthesis of α-quaternary propargylic-substituted is still much less developed, and preprepared nucleophiles are generally applied in this type reaction with substrates, which limits efficiency diversity obtained products. Herein, we disclose unprecedented three-component α-diazo esters amines carbonates under dirhodium/palladium dual catalysis. The key success multicomponent avoid two-component side reactions through tandem process dirhodium(II)-catalyzed carbene insertion palladium-catalyzed regiodivergent substitution. judicious selection diphosphine (dppf) or monophosphine (tBuBrettphos) as ligand crucial for different switchable way, 1,3-dienyl propargylated products, high regio- chemoselectivities.

Language: Английский

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Transition Metal‐Catalyzed Dearomative Vinylation of Electron Rich Benzenes, Naphthalenes and Indoles with Alkynes

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(3), P. 270 - 294

Published: Jan. 10, 2023

Abstract Dearomatization reactions are among the most efficient chemical processes, combining atom economy, stereospecificity and ability to generate molecular complexity in a single step. Dearomative vinylation provide synthetic connection between readily available, simple aromatic starting materials more unsaturated alkynes. The last decade has witnessed steady increase development of transition metal‐catalyzed dearomative methods electron rich compounds with alkynes, providing new approaches high‐value building blocks natural products. This review aims serve as comprehensive reference for work magnified image

Language: Английский

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Gold-catalyzed four-component multifunctionalization of alkynes

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: June 15, 2023

The alkyne unit is a versatile building block in organic synthesis and the development of selective multifunctionalization alkynes an important object research this field. Herein, we report interesting gold-catalyzed, four-component reaction that achieves oxo-arylfluorination or oxo-arylalkenylation internal aromatic aliphatic alkynes, efficiently breaking carbon-carbon triple bond forming four new chemical bonds. divergence can be controlled by site-directing functional groups alkynes; presence phosphonate favors oxo-arylfluorination, while carboxylate motif benefits oxo-arylalkenylation. This enabled Au(I)/Au(III) redox coupling process using Selectfluor as both oxidant fluorinating reagent. A wide range structurally diverse α,α-disubstituted ketones, tri- tetra-substituted unsaturated ketones have been prepared synthetically valuable yields with excellent chemo-, regio- stereoselectivity. gram-scale preparation late-stage application complex further enhanced their synthetic value.

Language: Английский

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