Transformable Transient Directing Group-Assisted C(sp2)–H Activation: Synthesis and Late-Stage Functionalizations of o-Alkenylanilines DOI
Bubul Das, Anjali Dahiya, Ashish Kumar Sahoo

и другие.

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(19), С. 13383 - 13388

Опубликована: Сен. 14, 2022

The isocyanate group in aryl isocyanates serves as a transformable transient directing Ru(II)-catalyzed ortho olefination leading to o-alkenylanilines. In alcoholic solvents, are transformed into carbamates, which initiate the insertion of acrylates via o-C-H activation. particular, tAmOH dual role solvent-cum mediator. o-alkenylanilines converted azacoumarins and subsequently C-4 aryl-substituted using iodides coupling partners Pd(II)-catalyzed C-H functionalizations.

Язык: Английский

Transition‐Metal‐Catalyzed, Chelation‐Assisted C−H Alkenylation and Allylation of Organic Molecules with Unactivated Alkenes DOI

Ravichandran Logeswaran,

Masilamani Jeganmohan

Advanced Synthesis & Catalysis, Год журнала: 2022, Номер 364(13), С. 2113 - 2139

Опубликована: Май 6, 2022

Abstract Olefins are important building blocks and widely utilized in synthetic organic chemistry. Owing to its omnipresence unique reactivity, the functionalization of alkenes has become a powerful method for constructing complex molecules. In this context, direct chelation‐assisted C−H olefination at inert bonds represents most straightforward introducing alkenyl group into compounds highly regio‐ stereoselective manner. Despite remarkable advances reaction, successful transformations restricted activated or electronically biased olefins such as acrylates, styrenes, acrylamides, vinyl sulfones, phosphonates. Literature reports on with unactivated unbiased limited due poor intrinsic reactivity regioselectivity issues. significant challenges, past few years have witnessed tremendous growth. The present review describes recent allylation aromatics, alkenes, heteroaromatics via concerted‐metallation‐ deprotonation pathway.Transition metals palladium, rhodium, iridium cobalt used these kind transformations. scope, mechanistic investigation, limitation alkenylation reactions discussed elaborately. includes all reported base‐assisted pathway. magnified image

Язык: Английский

Процитировано

33
Looking deep into C–H functionalization: the synthesis and application of cyclopentadienyl and related metal catalysts DOI
Guilherme A. M. Jardim, Renato L. Carvalho, Mateus P. Nunes

и другие.

Chemical Communications, Год журнала: 2022, Номер 58(19), С. 3101 - 3121

Опубликована: Янв. 1, 2022

This feature review is focused on recent key applications of commonly used transition-metal Cp-type catalysts for C–H bond functionalizations.

Язык: Английский

Процитировано

23
Recent advances in rhodium-catalysed cross-dehydrogenative-coupling between two C(sp2)–H bonds DOI

Yi Ling Tsang,

Pui Ying Choy, Man Pan Leung

и другие.

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(7), С. 1992 - 2012

Опубликована: Янв. 1, 2022

A comprehensive review overviewing the advances in Rh-catalyzed cross-dehydrogenative-coupling period of 2016–2021 is presented.

Язык: Английский

Процитировано

21
Scandium-Catalyzed Benzylic C(sp3)–H Alkenylation of Tertiary Anilines with Alkynes DOI
Xian Xu,

Qianlin Sun,

Xin Xu

и другие.

Organic Letters, Год журнала: 2022, Номер 24(22), С. 3970 - 3975

Опубликована: Май 31, 2022

This work describes the chemo- and stereoselective benzylic C(sp3)-H alkenylation of tertiary ortho-methyl anilines with internal alkynes using a simple β-diketiminato scandium catalyst. protocol offers an efficient method for synthesis new family ortho-allylanilines in high yields. The resultant products facilely underwent further chemical transformation to other valuable anilines. A cationic benzyl species was isolated from stoichiometric reaction confirmed be catalytic intermediate.

Язык: Английский

Процитировано

14
Synthesis of allylanilines via scandium-catalysed benzylic C(sp3)–H alkenylation with alkynes DOI
Wei Zhou, Xuefeng Cong, Masayoshi Nishiura

и другие.

Chemical Communications, Год журнала: 2022, Номер 58(52), С. 7257 - 7260

Опубликована: Янв. 1, 2022

The ortho-selective benzylic C(sp3)-H alkenylation of 2-methyl tertiary anilines with internal alkynes has been achieved for the first time by using a half-sandwich scandium catalyst. This protocol provides straightforward route synthesis new family 2-allylaniline derivatives, featuring broad substrate scope, 100% atom-efficiency, high yields, and chemo-, regio-, stereoselectivity.

Язык: Английский

Процитировано

11
DFT Study on Mechanism of Ni–Al Bimetallic-Catalyzed C–H Cyclization to Construct Tricyclic Imidazoles: Roles of NHC Ligand and AlMe3 DOI
Cong Zhang, Guorong Li,

Zhenfeng Shang

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(3), С. 1505 - 1514

Опубликована: Янв. 13, 2024

The mechanism of the Ni–Al bimetallic-catalyzed C–H cyclization to construct tricyclic imidazoles is investigated using density functional theory calculations. calculation result shows that reaction involves sequential steps substrate coordination, ligand-to-ligand hydrogen transfer (LLHT), and C–C reductive elimination produce final product imidazole. LLHT step calculated be rate-determining step. oxidative addition benzimidazole bond Ni center insertion alkene into Ni–H occur concertedly in effects N-heterocyclic carbene (NHC) ligands AlMe3 on reactivity regioselectivity were also analyzed. These results shed light some ambiguous suggestions from experiments.

Язык: Английский

Процитировано

1
Asymmetric synthesis of cyclopenta[b]indoles via organocatalytic formal (3 + 2) cyclization of β-keto ester with azonaphthalene DOI

Yanji Song,

Shi Tang,

Qianping Chen

и другие.

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(11), С. 2734 - 2739

Опубликована: Янв. 1, 2023

Enantioselective formal (3 + 2) cyclization of cyclic β-keto esters with azonaphthalenes to synthesize cyclopenta[ b ]indoles in good yields high diastereo- and enantioselectivity is established by using guanidine-amides as catalysts under mild reaction conditions.

Язык: Английский

Процитировано

3
Ni(ii)-catalyzed C–H hydroarylation of diarylacetylenes with imidazolium salts DOI
Tianbao Wang, Xuesong Zheng,

Qinze Zheng

и другие.

Chemical Communications, Год журнала: 2022, Номер 58(16), С. 2730 - 2733

Опубликована: Янв. 1, 2022

A simple Ni(II)-catalyzed C-H hydroarylation of diarylacetylenes with imidazolium salts without adding any ligand was developed. It provides a facile and efficient access to (E)-2-(1,2-diarylvinyl)imidazolium salts. The preliminary results indicate rare nonredox catalytic cycle Ni(II), complementary the common redox starting from Ni(0).

Язык: Английский

Процитировано

3
Transformable Transient Directing Group-Assisted C(sp2)–H Activation: Synthesis and Late-Stage Functionalizations of o-Alkenylanilines DOI
Bubul Das, Anjali Dahiya, Ashish Kumar Sahoo

и другие.

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(19), С. 13383 - 13388

Опубликована: Сен. 14, 2022

The isocyanate group in aryl isocyanates serves as a transformable transient directing Ru(II)-catalyzed ortho olefination leading to o-alkenylanilines. In alcoholic solvents, are transformed into carbamates, which initiate the insertion of acrylates via o-C-H activation. particular, tAmOH dual role solvent-cum mediator. o-alkenylanilines converted azacoumarins and subsequently C-4 aryl-substituted using iodides coupling partners Pd(II)-catalyzed C-H functionalizations.

Язык: Английский

Процитировано

3