Oxydiazomethylation of Alkenes via Photoredox Catalysis DOI

Ying Zeng,

Xiaochan Zheng,

Lixing Shen

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 12, 2024

α-Diazoesters belong to significantly important carbenoid precursors in synthetic chemistry. Diazomethylation-based difunctionalization of alkenes is highly valuable but remain nontrivial. Herein, we reported a general and modular approach for the direct 1,2-oxydiazomethylation through visible-light photoredox catalysis. This process exploits photocatalyzed strategy convert γ-formyloxyl-α-diazoesters using α-diazo iodonium salts as carbyne precursors, featuring wide substrate tolerance broad late-stage diversifications. Mechanistic studies suggest that formation γ-carbocation-tethered α-diazoesters plays crucial role trapping DMF H

Language: Английский

Rh-catalyzed double carbonylation of cyclopropenes toward valerolactone derivatives via cleavage of carbon–carbon double bonds DOI

Song‐Zhou Cai,

Can Li,

Suliang Wang

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

Language: Английский

Citations

1
Recent Advances in Nickel Catalyzed Carbonylative Reactions via the Insertion of Carbon Monoxide† DOI
Xinzhou Chen, Gang Chen, Zhong Lian

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 42(2), P. 177 - 189

Published: Sept. 4, 2023

Comprehensive Summary Carbonyl compounds have attracted considerable attention due to their extensive applications in drug discovery. Furthermore, they are important synthetic intermediates for the construction of carbon‐carbon and carbon‐heteroatom bonds. Transition‐metal‐catalyzed carbonylation via insertion CO is one most efficient straightforward strategies access carbonyl compounds. However, transition‐metal‐catalyzed carbonylative reactions require expensive toxic noble‐metal catalysts. Therefore, there a growing demand exploration nickel‐catalyzed earth abundance low cost nickel. Compared with well‐established palladium‐catalyzed reactions, analogous transformations been relatively underdeveloped. This primarily because strongly binds nickel, often resulting catalyst poisoning. In recent years, some research groups focused on using surrogates or NN 2 pincer nickel circumvent formation Ni(CO) 4 . Nickel‐catalyzed has applied carbonyl‐containing compounds, such as ketones, carboxylic acids, thioesters, acyl chloride carboxamides.

Language: Английский

Citations

23
Copper-Catalyzed Hydroamination: Enantioselective Addition of Pyrazoles to Cyclopropenes DOI
Minghao Wang,

Julie Simon,

Mengfei Xu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(27), P. 14573 - 14580

Published: June 30, 2023

Chiral N-cyclopropyl pyrazoles and structurally related heterocycles are prepared using an earth-abundant copper catalyst under mild reaction conditions with high regio-, diastereo-, enantiocontrol. The observed N2:N1 regioselectivity favors the more hindered nitrogen of pyrazole. Experimental DFT studies support a unique mechanism that features five-centered aminocupration.

Language: Английский

Citations

22
Manganese-Catalyzed Carbonylation of Unactivated Alkyl Bromides with Alkylidenecyclopropanes DOI

Peng-Rui Liu,

Miao-Miao Ji,

Jian-Bang Hu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(12), P. 9487 - 9495

Published: June 7, 2024

Language: Английский

Citations

8
Nickel‐Catalyzed Enantioconvergent Carboxylation Enabled by a Chiral 2,2′‐Bipyridine Ligand DOI
Linghua Wang, Tao Li, Saima Perveen

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(51)

Published: Oct. 27, 2022

In contrast to previous approaches chiral α-aryl carboxylic acids that based on reactions using hazardous gases, pressurized setup and mostly noble metal catalysts, in this work, a nickel-catalyzed general, efficient highly enantioselective carboxylation reaction of racemic benzylic (pseudo)halides under mild conditions atmospheric CO2 has been developed. A unique 2,2'-bipyridine ligand named Me-SBpy featuring compact polycyclic skeleton enabled both high reactivity stereoselectivity. The utility method demonstrated by synthesis various (30 examples, up 95 % yield 99 : 1 er), including profen family anti-inflammatory drugs transformations the as key intermediates. Based mechanistic experimental results, plausible catalytic cycle involving Ni-complex/radical equilibrium Lewis acid-assisted activation proposed.

Language: Английский

Citations

28
Diastereo‐ and Enantioselective Hydrophosphination of Cyclopropenes under Lanthanocene Catalysis DOI
Xiaobin Lin, Kun An, Qingde Zhuo

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(34)

Published: July 5, 2023

Abstract The asymmetric hydrophosphination of cyclopropenes with phosphines is much interest and importance, but has remained hardly explored to date probably because the lack suitable catalysts. We report here diastereo‐ enantioselective 3,3‐disubstituted by a chiral lanthanocene catalyst bearing C 2 ‐symmetric 5,6‐dioxy‐4,7‐ trans ‐dialkyl‐substituted tetrahydroindenyl ligands. This protocol offers selective efficient route for synthesis new family phosphinocyclopropane derivatives, featuring 100 % atom efficiency, good enantioselectivity, broad substrate scope, no need directing group.

Language: Английский

Citations

14
Enantioselective Synthesis of Cyclopropanes via CuH-Catalyzed Intramolecular Hydroalkylation DOI

Giovanni Lonardi,

S Franco,

Mattia Sartorello

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8730 - 8738

Published: May 21, 2024

A Cu-catalyzed cyclopropanation of γ-bromocrotonate derivatives via a hydrocupration–alkylation sequence is described. This hydroalkylation process good generality and allows access to chiral cyclopropanes bearing aryl, heteroaryl, N-indole, alkenyl, alkyl substituents, all with complete trans-diastereoselectivity, enantioselectivities up >99:1 er, high yields. An experimental computational mechanistic analysis was undertaken, which provided full understanding the factors affecting reaction's diastereo- enantioselectivity. More specifically, it found that Cu-catalyst drives both conjugate hydride addition alkylation steps reaction enantioselectivity governed by distortion effects metal coordination sphere at diastereomeric TSs.

Language: Английский

Citations

6
Enantioconvergent synthesis of axially chiral amides enabled by Pd-catalyzed dynamic kinetic asymmetric aminocarbonylation DOI Creative Commons
Lei Su,

Shen Gao,

Jiawang Liu

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 23, 2024

Atropisomeric biaryls bearing carbonyl groups have attracted increasing attention due to their prevalence in diverse bioactive molecules and crucial role as efficient organo-catalysts or ligands asymmetric transformations. However, preparation often involves tedious multiple steps, the direct synthesis via carbonylation has scarcely been investigated. Herein, we report an palladium-catalyzed enantioconvergent aminocarbonylation of racemic heterobiaryl triflates with amines dynamic kinetic transformation (DyKAT). This protocol features a broad substrate scope excellent compatibility for rapid construction axially chiral amides good high yields enantioselectivities. Detailed mechanistic investigations discover that base can impede intramolecular hydrogen bond-assisted axis rotation products, thus allowing success achieve enantioselectivity. Moreover, achieved be directly utilized N,N,N-pincer copper-catalyzed enantioselective formation C(sp3)-N C(sp3)-P bonds. Axially containing not only exist various drug candidates but also serve authors transformation.

Language: Английский

Citations

6
Pd‐Catalyzed Asymmetric 5‐exo‐trig Cyclization/Cyclopropanation/Carbonylation of 1,6‐Enynes for the Construction of Chiral 3‐Azabicyclo[3.1.0]hexanes DOI
Qiu‐Yu Li, Yunchu Zhang,

Pengyun Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(4)

Published: Nov. 25, 2022

We herein disclose a mild and efficient access to chiral 3-azabicyclo[3.1.0]hexanes via Pd-catalyzed asymmetric 5-exo-trig cyclization/cyclopropanation/carbonylation of 1,6-enynes. Various nucleophiles, such as alcohols, phenols, amines water, are well compatible with the reaction system. This forms three C-C bonds, two rings, adjacent quaternary carbon stereocenters one C-O/C-N bond excellent regio- enantioselectivities. The products could be further functionalized generate library 3-azabicyclo[3.1.0]hexane frameworks.

Language: Английский

Citations

21
Facile Synthesis of Chiral α‐Hydroxy Ketones by a Ni‐Catalyzed Multicomponent Hydrometallation–CO Insertion–Enantioconvergent Alkylation Cascade DOI
Jian Chen,

Gao Deng,

You Wang

et al.

Chinese Journal of Chemistry, Journal Year: 2022, Volume and Issue: 41(3), P. 294 - 300

Published: Oct. 17, 2022

Comprehensive Summary NiH‐catalyzed multicomponent reductive hydrofunctionalization of alkenes is an attractive but poorly explored approach to rapidly increasing molecular complexity. In this process, the selective generation desired product can be challenging. Herein, we report that a highly chemo‐, regio‐ and enantioselective hydrocarbonylation has been achieved using chloroformate ester as source CO. A wide range structurally diverse α‐hydroxy ketones, privileged structural elements in bioactive molecules useful building blocks, were obtained from such reactions with high enantiomeric purity.

Language: Английский

Citations

20