A Carbene Relay Strategy for Cascade Insertion Reactions DOI
Li Li,

Chenggang Mi,

Guanwang Huang

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(45)

Опубликована: Сен. 19, 2023

Abstract Insertion reactions that involve stabilized electrophilic metallocarbenes are of great importance for installing α‐heteroatoms to carbonyl compounds. Nevertheless, the limited availability carbene precursors restricts introduction only a single heteroatom. In this report, we describe new approach based on an I (III) /S (VI) reagent promotes cascade insertion heteroatoms. This is achieved by sequentially generating two α‐heteroatom‐substituted metal carbenes in one reaction. We found mixed ylide reacts efficiently with transition catalyst and X−H bond (where X=O, N). transformation leads sequential formation sulfoxonium‐ X‐substituted Rh‐carbenes, enabling further another Y−H bond. Remarkably, wide range symmetrical unsymmetrical α,α‐ O , ‐, N ‐subsituted ketones can be prepared under mild ambient conditions. addition, successfully demonstrated other cascades, such as CN/CN double amidation, C−H/C−S insertion, C−S/Y−H Y=S, N, O, C). Notably, latter cascades enabled simultaneous installation three functional groups α‐carbon compounds step. These demonstrate versatility our approach, allowing synthesis esters multiple using common precursor.

Язык: Английский

Recent advances in transition-metal-catalyzed carbene insertion to C–H bonds DOI
Yuan He, Zilong Huang, Kaikai Wu

и другие.

Chemical Society Reviews, Год журнала: 2022, Номер 51(7), С. 2759 - 2852

Опубликована: Янв. 1, 2022

C-H functionalization has been emerging as a powerful method to establish carbon-carbon and carbon-heteroatom bonds. Many efforts have devoted transition-metal-catalyzed direct transformations of Metal carbenes generated in situ from transition-metal compounds diazo or its equivalents are usually applied the transient reactive intermediates furnish catalytic cycle for new C-C C-X bond formation. Using this strategy unactivated simple alkanes complex molecules can be further functionalized transformed multi-functionalized compounds. In area, carbene insertion bonds paid continuous attention. Diverse catalyst design strategies, synthetic methods, potential applications developed. This critical review will summarize advance dated up July 2021, by categories aliphatic C(sp3)-H, aryl (aromatic) C(sp2)-H, heteroaryl (heteroaromatic) C(sp2)-H bonds, alkenyl alkynyl C(sp)-H, well asymmetric more coverage given recent work. Due rapid development future directions topic also discussed. give authors an overview chemistry with focus on systems

Язык: Английский

Процитировано

230
A heterogeneous iridium single-atom-site catalyst for highly regioselective carbenoid O–H bond insertion DOI
Jie Zhao,

Shufang Ji,

Chenxi Guo

и другие.

Nature Catalysis, Год журнала: 2021, Номер 4(6), С. 523 - 531

Опубликована: Июнь 21, 2021

Язык: Английский

Процитировано

140
RuII-Catalyzed/NH2-Assisted Selective Alkenyl C–H [5 + 1] Annulation of Alkenylanilines with Sulfoxonium Ylides to Quinolines DOI
Pu Chen, Jiang Nan, Yan Hu

и другие.

Organic Letters, Год журнала: 2019, Номер 21(12), С. 4812 - 4815

Опубликована: Июнь 13, 2019

A novel ruthenium-catalyzed [5 + 1] annulation of 2-alkenylanilines with sulfoxonium ylides was developed for the rapid assembly highly functionalized quinolines. This new catalytic process employs challenging but synthetically ideal free amino functionality to achieve alkenyl C–H activation as one-carbon coupling partners. Various 2-acylquinolines could be obtained good yields and excellent functional group tolerance. Moreover, potential synthetic application this methodology exemplified by several chemical transformations.

Язык: Английский

Процитировано

105
Recent advances in Rh(iii)/Ir(iii)-catalyzed C–H functionalization/annulation via carbene migratory insertion DOI
Sanjeev Kumar, Saiprasad Nunewar,

Srilekha Oluguttula

и другие.

Organic & Biomolecular Chemistry, Год журнала: 2021, Номер 19(7), С. 1438 - 1458

Опубликована: Янв. 1, 2021

The review highlighted diverse annulations, including nitrogen, oxygen, sulfur heterocycles and carbocylizations via Rh(iii)/Ir(iii)-catalyzed C–H functionalization/annulation with various arene carbene precursors.

Язык: Английский

Процитировано

90
Application of sulfoxonium ylide in transition-metal-catalyzed C-H bond activation and functionalization reactions DOI
Anil Kumar, Mahadev Sharanappa Sherikar, Vinayak Hanchate

и другие.

Tetrahedron, Год журнала: 2021, Номер 101, С. 132478 - 132478

Опубликована: Окт. 8, 2021

Язык: Английский

Процитировано

70
Rh(III)-Catalyzed Chemodivergent Annulations between Indoles and Iodonium Carbenes: A Rapid Access to Tricyclic and Tetracyclic N-Heterocylces DOI
Saiprasad Nunewar, Sanjeev Kumar,

Harishchandra Pandhare

и другие.

Organic Letters, Год журнала: 2021, Номер 23(11), С. 4233 - 4238

Опубликована: Май 21, 2021

Herein, we report an acid-controlled highly tunable selectivity of Rh(III)-catalyzed [4 + 2] and [3 3] annulations N-carboxamide indoles with iodonium ylides lead to form synthetically important tricyclic tetracyclic N-heterocycles. Here, ylide serves as a carbene precursor. The protocol proceeds under operationally simple conditions provides novel scaffolds such 3,4-dihydroindolo[1,2-c]quinazoline-1,6(2H,5H)-dione 1H-[1,3]oxazino[3,4-a]indol-1-one derivatives broad range functional group tolerance moderate excellent yields. Furthermore, the synthetic utility was extended for various chemical transformations easily scaled up large-scale level.

Язык: Английский

Процитировано

69
Co(III), Rh(III) & Ir(III)‐Catalyzed Direct C−H Alkylation/Alkenylation/Arylation with Carbene Precursors DOI
Saiprasad Nunewar, Sanjeev Kumar,

Srilakshmi Talakola

и другие.

Chemistry - An Asian Journal, Год журнала: 2021, Номер 16(5), С. 443 - 459

Опубликована: Янв. 15, 2021

Metal carbenes play a pivotal role in transition-metal-catalyzed synthetic transfer reactions. The metal carbene is generated either from diazo compound through facile extrusion of N2 with catalyst or situ other sources like triazoles, pyriodotriazoles, sulfoxonium ylides and iodonium-ylide. On the hand, Co(III), Rh(III) & Ir(III)-catalyzed C-H functionalizations have been well established as key step to enable construction various transformations. Interestingly, recent years, merging these two concepts activation migratory insertion gained much attention, particular group 9 metal-catalyzed arene precursors via insertion. In this review, we summarize advances direct alkylation/alkenylation/arylation also discuss intermediates within catalytic cycles.

Язык: Английский

Процитировано

66
Photocatalytic gem‐Difluoroolefination Reactions by a Formal C−C Coupling/Defluorination Reaction with Diazoacetates DOI

Fang Li,

Chao Pei, René M. Koenigs

и другие.

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(4)

Опубликована: Окт. 30, 2021

The photolysis of diazoalkanes to conduct singlet carbene transfer reactions colored has recently attracted significant interest in organic synthesis. Herein, we describe a photocatalytic approach that allows the access triplet intermediates via energy highly efficient gem-difluoroolefination with α-trifluoromethyl styrenes. use tertiary amines proved pivotal unlock this unusual reaction pathway and prevent undesired cyclopropanation pathways. amine further facilitates ultimate abstraction fluoride yield gem-difluoroolefins (43 examples, up 88 % yield), which is supported by experimental theoretical mechanistic studies. We explored synthesis method broad substrate scope, ranging from simple olefins heterocyclic towards decoration pharmaceutically relevant building blocks.

Язык: Английский

Процитировано

62
Running Wild through Dirhodium Tetracarboxylate-Catalyzed Combined CH(C)-Functionalization/Cope Rearrangement Landscapes: Does Post-Transition-State Dynamic Mismatching Influence Product Distributions? DOI
Wentao Guo, Dean J. Tantillo

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(10), С. 7039 - 7051

Опубликована: Фев. 28, 2024

A special type of C–H functionalization can be achieved through insertion combined with Cope rearrangement (CHCR) in the presence dirhodium catalysts. This reaction was studied using density functional theory and ab initio molecular dynamics simulations, results which pointed to dynamic origins low yields observed some experiments. These studies not only reveal intimate details complex network underpinning CHCR reactions but also further cement generality importance nonstatistical effects controlling Rh2L4-promoted reactions.

Язык: Английский

Процитировано

12
Recent Advances in the Synthesis of Nitrogen Heterocycles Using Arenediazonium Salts as Nitrogen Sources DOI
Jidan Liu,

Jinyuan Jiang,

Liyao Zheng

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2020, Номер 362(22), С. 4876 - 4895

Опубликована: Авг. 4, 2020

Abstract Nitrogen heterocycles are important structural subunits that occur widely in bioactive natural products, pharmaceuticals, agrochemicals, dyes, cosmetics, and functional materials. Considering the importance of these useful compounds modern science, synthesis N‐heterocycles their derivatives has always been a hot topic organic synthesis. Recently, arenediazonium salts which can be easily prepared from inexpensive abundantly available anilines, have used as versatile nitrogen sources field heterocycle synthetic chemistry due to ready availability, rich reactivity, diverse transformations. The aim present review is summarize recent advances using past ten years. Hopefully, it provide practical guidance for readers who interested utilizing building blocks For simplicity clarity, organization this based on number N atoms ring heterocycle. magnified image

Язык: Английский

Процитировано

68