Why is the Ir(III)-Mediated Amido Transfer Much Faster Than the Rh(III)-Mediated Reaction? A Combined Experimental and Computational Study DOI
Yoonsu Park, Joon Heo, Mu‐Hyun Baik

et al.

Journal of the American Chemical Society, Journal Year: 2016, Volume and Issue: 138(42), P. 14020 - 14029

Published: Oct. 3, 2016

The mechanism of the Ir(III)- and Rh(III)-mediated C–N coupling reaction, which is key step for catalytic C–H amidation, was investigated in an integrated experimental computational study. Novel amidating agents containing a 1,4,2-dioxazole moiety allowed designing stoichiometric version reaction giving access to intermediates that reveal details about each reaction. Both DFT kinetic studies strongly point where M(III)-complex engages agent via oxidative form M(V)–imido intermediate, then undergoes migratory insertion afford final coupled product. For first time, versions Ir- Rh-mediated amidation were compared systematically other. Iridium reacts much faster than rhodium (∼1100 times at 6.7 °C) with being so fast activation initial Ir(III)-complex becomes rate-limiting. In case Rh, Rh–imido formation These qualitative differences stem from unique bonding feature dioxazole relativistic contraction Ir(V), affords more favorable energetics full molecular orbital analysis presented rationalize explain electronic features govern this behavior.

Language: Английский

Transition Metal-Catalyzed C–H Amination: Scope, Mechanism, and Applications DOI
Yoonsu Park,

Youyoung Kim,

Sukbok Chang

et al.

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(13), P. 9247 - 9301

Published: Jan. 4, 2017

Catalytic transformation of ubiquitous C-H bonds into valuable C-N offers an efficient synthetic approach to construct N-functionalized molecules. Over the last few decades, transition metal catalysis has been repeatedly proven be a powerful tool for direct conversion cheap hydrocarbons synthetically versatile amino-containing compounds. This Review comprehensively highlights recent advances in intra- and intermolecular amination reactions utilizing late metal-based catalysts. Initial discovery, mechanistic study, additional applications were categorized on basis scaffolds types reactions. Reactivity selectivity novel systems are discussed three sections, with each being defined by proposed working mode.

Language: Английский

Citations

1921
Palladium-Catalyzed Transformations of Alkyl C–H Bonds DOI
Jian He, Masayuki Wasa,

Kelvin S. L. Chan

et al.

Chemical Reviews, Journal Year: 2016, Volume and Issue: 117(13), P. 8754 - 8786

Published: Dec. 2, 2016

This Review summarizes the advancements in Pd-catalyzed C(sp3)-H activation via various redox manifolds, including Pd(0)/Pd(II), Pd(II)/Pd(IV), and Pd(II)/Pd(0). While few examples have been reported of alkane C-H bonds, many activation/C-C C-heteroatom bond forming reactions developed by use directing group strategies to control regioselectivity build structural patterns for synthetic chemistry. A number mono- bidentate ligands also proven be effective accelerating directed weakly coordinating auxiliaries, which provides great opportunities reactivity selectivity (including enantioselectivity) functionalization reactions.

Language: Английский

Citations

1861
Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds DOI
Supriya Rej, Yusuke Ano, Naoto Chatani

et al.

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(3), P. 1788 - 1887

Published: Jan. 6, 2020

During the past decades, synthetic organic chemistry discovered that directing group assisted C–H activation is a key tool for expedient and siteselective construction of C–C bonds. Among various strategies, bidentate groups are now recognized as one most efficient devices selective functionalization certain positions due to fact its metal center permits fine, tunable, reversible coordination. The family permit types assistance be achieved, such N,N-dentate, N,O-dentate, N,S-dentate auxiliaries, which categorized based on coordination site. In this review, we broadly discuss bond reactions formation bonds with aid groups.

Language: Английский

Citations

812
Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C–H Bonds Elaboration DOI Creative Commons
Luca Capaldo, Davide Ravelli, Maurizio Fagnoni

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1875 - 1924

Published: Aug. 6, 2021

Direct photocatalyzed hydrogen atom transfer (d-HAT) can be considered a method of choice for the elaboration aliphatic C–H bonds. In this manifold, photocatalyst (PCHAT) exploits energy photon to trigger homolytic cleavage such bonds in organic compounds. Selective bond may achieved by judicious abstractor (key parameters are electronic character and molecular structure), as well reaction additives. Different classes PCsHAT available, including aromatic ketones, xanthene dyes (Eosin Y), polyoxometalates, uranyl salts, metal-oxo porphyrin tris(amino)cyclopropenium radical dication. The processes (mainly C–C formation) most cases carried out under mild conditions with help visible light. aim review is offer comprehensive survey synthetic applications d-HAT.

Language: Английский

Citations

801
Transition-Metal-Catalyzed, Coordination-Assisted Functionalization of Nonactivated C(sp3)–H Bonds DOI
Bin Liu, Andrew M. Romine, Camille Rubel

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(24), P. 14957 - 15074

Published: Oct. 29, 2021

Transition-metal-catalyzed, coordination-assisted C(sp3)–H functionalization has revolutionized synthetic planning over the past few decades as use of these directing groups allowed for increased access to many strategic positions in organic molecules. Nonetheless, several challenges remain preeminent, such requirement high temperatures, difficulty removing or converting groups, and, although metals provide some reactivity, employing outside palladium. This review aims give a comprehensive overview coordination-assisted, transition-metal-catalyzed, direct nonactivated bonds by covering literature since 2004 order demonstrate current state-of-the-art methods well limitations. For clarity, this been divided into nine sections transition metal catalyst with subdivisions type bond formation. Synthetic applications and reaction mechanism are discussed where appropriate.

Language: Английский

Citations

367
Construction of Quaternary Stereocenters by Palladium‐Catalyzed Carbopalladation‐Initiated Cascade Reactions DOI
Yuanyuan Ping, Yuxiu Li, Jieping Zhu

et al.

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(6), P. 1562 - 1573

Published: June 30, 2018

Abstract The enantioselective synthesis of molecules containing quaternary stereocenters is a field intense research interest and development. Among the known organic transformations, carbopalladation‐initiated domino transformations constitutes general method for construction compounds cyclic or spiro stereocenters. In this Minireview, recent achievements in palladium‐catalyzed Heck/C−H functionalizations developments processes are summarized.

Language: Английский

Citations

347
Site-selective C–H arylation of primary aliphatic amines enabled by a catalytic transient directing group DOI
Yongbing Liu, Haibo Ge

Nature Chemistry, Journal Year: 2016, Volume and Issue: 9(1), P. 26 - 32

Published: Sept. 12, 2016

Language: Английский

Citations

294
Manganese‐Catalyzed C−H Alkynylation: Expedient Peptide Synthesis and Modification DOI
Zhixiong Ruan,

Nicolas Sauermann,

Elisabetta Manoni

et al.

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(12), P. 3172 - 3176

Published: Feb. 9, 2017

Abstract Manganese(I)‐catalyzed C−H alkynylations with organic halides occurred unparalleled substrate scope, and thus enabled step‐economical functionalizations silyl, aryl, alkenyl, alkyl haloalkynes. The versatility of the manganese(I) catalysis manifold couplings haloalkynes featuring, among others, fluorescent labels, steroids, amino acids, thereby setting stage for peptide ligation as well efficient molecular assembly acyclic cyclic peptides. A plausible catalytic cycle was proposed.

Language: Английский

Citations

278
Recent advances in copper-mediated chelation-assisted functionalization of unactivated C–H bonds DOI
Wei‐Hao Rao, Bing‐Feng Shi

Organic Chemistry Frontiers, Journal Year: 2016, Volume and Issue: 3(8), P. 1028 - 1047

Published: Jan. 1, 2016

Recent advances in copper-mediated (both stoichiometric and catalytic) chelation-assisted functionalization of unactivated C–H bonds are reviewed.

Language: Английский

Citations

242
Transition-Metal-Catalyzed C–H Bond Activation for the Formation of C–C Bonds in Complex Molecules DOI Creative Commons
Jamie H. Docherty,

Thomas M. Lister,

Gillian McArthur

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(12), P. 7692 - 7760

Published: May 10, 2023

Site-predictable and chemoselective C–H bond functionalization reactions offer synthetically powerful strategies for the step-economic diversification of both feedstock fine chemicals. Many transition-metal-catalyzed methods have emerged selective activation bonds. However, challenges regio- chemoselectivity with application to highly complex molecules bearing significant functional group density diversity. As molecular complexity increases within structures risks catalyst intolerance limited applicability grow number groups potentially Lewis basic heteroatoms. Given abundance bonds already diversified such as pharmaceuticals, natural products, materials, design selection reaction conditions tolerant catalysts has proved critical successful direct functionalization. such, innovations formation carbon–carbon been discovered developed overcome these limitations. This review highlights progress made metal-catalyzed C–C forming including alkylation, methylation, arylation, olefination targets.

Language: Английский

Citations

228