Construction of C−S and C−Se Bonds from Unstrained Ketone Precursors under Photoredox Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(8)

Published: Jan. 8, 2024

A mild photoredox catalyzed construction of sulfides, disulfides, selenides, sulfoxides and sulfones from unstrained ketone precursors is introduced. Combination this deacylative process with S

Language: Английский

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Controllable skeletal reorganizations in natural product synthesis

Natural Product Reports, Journal Year: 2024, Volume and Issue: 41(2), P. 251 - 272

Published: Jan. 1, 2024

Covering: 2016 to 2023The synthetic chemistry community is always in pursuit of efficient routes natural products. Among the many available general strategies, skeletal reorganization, which involves formation, cleavage, and migration C-C C-heteroatom bonds, stands out as a particularly useful approach for assembly molecular skeletons. In addition, it allows late-stage modification products quick access other family members or unnatural derivatives. This review summarizes syntheses steroid, terpenoid, alkaloid that have been achieved by means this strategy past eight years. Our goal illustrate strategy's potency reveal spectacular human ingenuity demonstrated its use development.

Language: Английский

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DFT study on isothiourea-catalyzed C–C bond activation of cyclobutenone: the role of the catalyst and the origin of stereoselectivity

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(13), P. 2662 - 2669

Published: Jan. 1, 2024

The mechanism of organocatalytic C-C bond activation have been theoretically investigated.

Language: Английский

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Mechanism and Origin of Nickel-Catalyzed Decarbonylative Construction of C(sp²)–C(sp³) Bonds from Carboxylic Acids and Their Derivatives

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 31, 2025

Nickel-catalyzed arylation of carboxylic acids provides a ligand-controlled chemoselectivity-switchable method for the construction C(sp2)-C(sp3) bonds. Here, we employed density functional theory to provide detailed understanding mechanism and origin nickel-catalyzed carbonyl transformation. This reaction generates decarbonylation products through oxidative addition, activation C-C bonds, decarbonylation, binding alkyl radicals with Ni(III) complexes, final reduction elimination step. The bonds in aromatic carboxylate esters is more favorable than C-O bond because interaction between nickel catalyst π orbitals substrate's moiety during activation. induction effect ligand group together determines transfer tendency group.

Language: Английский

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Photocatalyzed Annulation‐Biselenylation of Enynone with Diarylselenides toward Biselenium‐Substituted 1‐Indanones under Metal‐ and Photosensitizer‐Free Conditions

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 17, 2025

Comprehensive Summary A practical photocatalytic annulation‐biselenylation strategy has been developed for the efficient synthesis of biselenium‐substituted 1‐indanones (38 examples in total) with generally good yields (up to 95%) and excellent stereoselectivity (>19 : 1 Z / E ratio) by employing enynones diaryl selenides as starting materials under photosensitizer‐free conditions. The reaction mechanism involves a cascade process comprising homolytic cleavage, radical addition, 5‐ exo ‐ dig cyclization, capture, enabling sequential formation multiple bonds, such C(sp 3 )‐Se, )‐C(sp 2 ), )‐Se rapidly construct molecular complexity. Notably, this approach demonstrates wide substrate compatibility tolerability towards various functional groups. It is further characterized its remarkable efficiency creating chemical bonds achieving high atomic utilization 100%.

Language: Английский

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Radical Addition-Enabled C–C σ-Bond Cleavage/Reconstruction to Access Functional Indanones: Total Synthesis of Carexane L

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 2913 - 2917

Published: April 3, 2024

C–C σ-bond cleavage and reconstruction is a significant tool for structural modification in synthetic chemistry but it remains formidable challenge to perform on unstrained skeletons. Herein, we describe radical addition-enabled cleavage/reconstruction reaction of allyl ketones access various functional indanones bearing benzylic quaternary center. The utility this method has been showcased by the first total synthesis carexane L, an indanone-based natural product.

Language: Английский

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Site-Selective C8-Alkylation of Quinolines with Cyclopropanols: Merging C–H/C–C Bond Activation

Organic Letters, Journal Year: 2023, Volume and Issue: 25(43), P. 7805 - 7809

Published: Oct. 23, 2023

The site-selective C8-alkylation of quinolines has been accomplished using cyclopropyl alcohols as the alkylating agents and N-oxide a weak chelating group in presence Co(III) catalysis via merging C-H/C-C bond activation. use cyclopropanol alkyl source, Co catalysis, substrate scope, HRMS analysis reaction intermediate, late-stage mutation drug molecules/natural products are important practical features.

Language: Английский

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Palladium‐Catalyzed Skeletal Reorganization of Cyclobutanones Invoving Successive C—C Bond/C—H Bond Cleavage

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(14), P. 1679 - 1683

Published: Feb. 22, 2023

Comprehensive Summary The utilization of cyclobutanones as the synthon in transition metal catalysis has been made great success. Because C(carbonyl)−C bond can be cleaved through strain release. Despite those advancements, main catalysts literature are Rh or Ni and reaction with C—H is still underdeveloped. Herein, we realized first palladium‐catalyzed skeletal reorganization involving successive cleavage bonds cleavage, which constitutes an rapid access to diverse indanones. In contrast previous Rh‐catalytic system, Pd‐catalytic system herein involves different mechanism features several advantages: 1) no need directing group facilitate cleavage; 2) much milder condition 3) simplified work‐up.

Language: Английский

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Construction of C−S and C−Se Bonds from Unstrained Ketone Precursors under Photoredox Catalysis

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(8)

Published: Jan. 5, 2024

Abstract A mild photoredox catalyzed construction of sulfides, disulfides, selenides, sulfoxides and sulfones from unstrained ketone precursors is introduced. Combination this deacylative process with S N 2 or coupling reactions provides novel convenient modular strategies toward unsymmetrical symmetric disulfides. Reactivity studies favor a bromine radical that initiates HAT (Hydrogen Atom Transfer) the aminal intermediate resulting in expulsion C‐centered intercepted to make C−S C−Se bonds. Gram scale reactions, broad substrate scope tolerance towards various functional groups render method appealing for future applications synthesis organosulfur selenium complexes.

Language: Английский

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Computational Exploration of 1,2-Carboamine Carbonylation Catalyzed by Nickel

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(7), P. 4484 - 4495

Published: March 12, 2024

Nickel-catalyzed carbonylation of alkenes is a stereoselective and regioselective method for the synthesis amide compounds. Theoretical predictions with density functional theory calculations revealed mechanism origin stereoselectivity regioselectivity nickel-catalyzed norbornene. The reaction proceeds through oxidative addition, migration insertion alkenes, subsequent reduction elimination to afford cis-carbonylation product. C–N bond activation amides unfavorable because addition ability C–C stronger than that bond. determining step migratory strained olefin. structural analysis shows steroselectivity controlled by steric hindrance methyl groups olefins substituents IMes in ligands.

Language: Английский

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