Manganese(I)‐Catalyzed Site‐Selective C6‐Alkenylation of 2‐Pyridones Using Alkynes via C−H Activation DOI
Shanhong Wan,

Zhenli Luo,

Xin Xu

et al.

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 363(10), P. 2586 - 2593

Published: March 9, 2021

Abstract A Mn(I)‐catalyzed chelation‐assisted direct C6−H alkenylation of 2‐pyridones with both terminal and internal alkynes in a highly regio‐ stereo‐selective manner has been developed. The catalytic system consisting Mn(CO) 5 Br catalyst KOAc additive allows 1‐(2‐pyridyl)‐2‐pyridones to undergo various methyl tert ‐butyl ether (MTBE) furnish the C6‐alkenylated 2‐pyridone products high yields, occurs CH 2 Cl at increased loadings. Mechanistic studies suggest involvement five‐membered organomanganese as key intermediate cycle. magnified image

Language: Английский

C–H Activation: Toward Sustainability and Applications DOI Creative Commons
Toryn Dalton,

Teresa Faber,

Frank Glorius

et al.

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(2), P. 245 - 261

Published: Feb. 2, 2021

Since the definition of "12 Principles Green Chemistry" more than 20 years ago, chemists have become increasingly mindful need to conserve natural resources and protect environment through judicious choice synthetic routes materials. The direct activation functionalization C–H bonds, bypassing intermediate functional group installation is, in abstracto, step atom economic, but numerous factors still hinder sustainability large-scale applications. In this Outlook, we highlight research areas seeking overcome challenges activation: pursuit abundant metal catalysts, avoidance static directing groups, replacement oxidants, introduction bioderived solvents. We close by examining progress made subfield aryl borylation from its origins, highly efficient precious Ir-based systems, emerging 3d catalysts. future growth field will depend on industrial uptake, thus urge researchers strive toward sustainable activation.

Language: Английский

Citations

575
Reactivity-Controlling Factors in Carboxylate-Assisted C–H Activation under 4d and 3d Transition Metal Catalysis DOI
Torben Rogge, João C. A. Oliveira, Rositha Kuniyil

et al.

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(18), P. 10551 - 10558

Published: Aug. 17, 2020

Detailed density functional theory calculations provide valuable insight into reactivity-controlling factors in transition metal-catalyzed C–H activation by carboxylate assistance. The chelation-assisted of a variety arenes 3d and 4d metal complexes was analyzed means bond order analysis through (DFT) as well energy decomposition DLPNO–CCSD(T) calculations, thereby providing in-depth information on distinct electronic influences the key state demonstrating preferred base-assisted internal electrophilic substitution (BIES) rather than concerted metalation-deprotonation (CMD) pathway.

Language: Английский

Citations

93
Unlocking Diverse π-Bond Enrichment Frameworks by the Synthesis and Conversion of Boronated Phenyldiethynylethylenes DOI

Jinhui Xie,

Wangyang Li, Yong Lu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 10167 - 10176

Published: March 27, 2024

The π-bond enrichment frameworks not only serve as a crucial building block in organic synthesis but also assume pivotal role the fields of materials science, biomedicine, photochemistry, and other related disciplines owing to their distinctive structural characteristics. incorporation various substituents into C═C double bonds tetrasubstituted alkenes is currently highly significant research area. However, with diverse on poses challenge achieving stereoselectivity. Here, we reported an efficient convergent route Cu-catalyzed borylalkynylation both symmetrical unsymmetrical 1,3-diynes, B2pin2, acetylene bromide construction boronated phenyldiethynylethylene (BPDEE) derivatives excellent chemo-, stereo-, regioselectivities. BPDEE could transform novel π-conjugated gem-diphenyldiethynylethylene (DPDEE), vinylphenyldiethynylethylene (VPDEE), phenyltriethynylethylene (PTEE) by stepwise process, which provides flexible platform for complex that were difficult synthesize previous methods. initial optical characterization revealed synthesized molecules exhibited aggregation-induced emission (AIE) properties, further establishes groundwork future applications enriches advances field functional research.

Language: Английский

Citations

14
Manganese complex-catalysed α-alkylation of ketones with secondary alcohols enables the synthesis of β-branched carbonyl compounds DOI Open Access
Satyadeep Waiba, Sayan K. Jana, Ayan Jati

et al.

Chemical Communications, Journal Year: 2020, Volume and Issue: 56(60), P. 8376 - 8379

Published: Jan. 1, 2020

Herein, β-branched carbonyl compounds were synthesised via the α-alkylation of ketones with secondary alcohols under "borrowing hydrogen" catalysis. A wide range alcohols, including various cyclic, acyclic, symmetrical, and unsymmetrical have been successfully applied developed reaction conditions. manganese(i) complex bearing a phosphine-free multifunctional ligand catalysed produced water as sole byproduct.

Language: Английский

Citations

57
Catalytic Alkyne Dimerization without Noble Metals DOI

Qiuming Liang,

Kasumi Hayashi,

Datong Song

et al.

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(9), P. 4895 - 4905

Published: April 1, 2020

1,3-Enynes are core structures of various natural products or pharmaceuticals and broadly used synthons in organic synthesis. Metal-catalyzed alkyne dimerization is a desirable preparation method, due to its perfect atom economy the readily available substrates. Controlling regio- stereoselectivity remains challenge, competing formation head-to-tail (gem) head-to-head (E/Z) isomers. Although catalytic systems based on noble metals have been extensively studied, there has growing interest replace these with environmentally benign inexpensive alternatives. In this Perspective, we highlight recent advances dimerization, without use metals.

Language: Английский

Citations

54
Additive-Controlled Divergent Synthesis of Tetrasubstituted 1,3-Enynes and Alkynylated 3H-Pyrrolo[1,2-a]indol-3-ones via Rhodium Catalysis DOI
Fei Zhao,

Xin Gong,

Yangbin Lu

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(3), P. 727 - 733

Published: Jan. 8, 2021

Herein, we report the additive-controlled divergent synthesis of tetrasubstituted 1,3-enynes and alkynylated 3H-pyrrolo[1,2-a]indol-3-ones through rhodium-catalyzed C-H alkenylation/DG migration [3+2] annulation, respectively. This protocol features rare directing group in 1,3-diyne-involved activation, excellent regio- stereoselectivity, monofunctionalization over difunctionalization, broad substrate scope, moderate to high yields, good functional compatibility, mild redox-neutral conditions.

Language: Английский

Citations

52
Recent advances and perspectives in manganese-catalyzed C–H activation DOI

Thaipparambil Aneeja,

Mohan Neetha, C. M. A. Afsina

et al.

Catalysis Science & Technology, Journal Year: 2020, Volume and Issue: 11(2), P. 444 - 458

Published: Dec. 10, 2020

Manganese-catalyzed C–H activation has become an emerging area in organic chemistry. These efficient and eco-friendly manganese catalysed reactions provides new opportunities the field of synthetic

Language: Английский

Citations

51
Nickel-catalyzed site- and stereoselective reductive alkylalkynylation of alkynes DOI Creative Commons
Yi Jiang,

Jiaoting Pan,

Tao Yang

et al.

Chem, Journal Year: 2021, Volume and Issue: 7(4), P. 993 - 1005

Published: Jan. 20, 2021

Language: Английский

Citations

43
Traceless Bidentate Directing Group Assisted Cobalt-Catalyzed sp2-C–H Activation and [4 + 2]-Annulation Reaction with 1,3-Diynes DOI
Arnab Dey, Chandra M. R. Volla

Organic Letters, Journal Year: 2020, Volume and Issue: 22(19), P. 7480 - 7485

Published: Sept. 16, 2020

An efficient cobalt-catalyzed [4 + 2] annulation of hydrazones and 1,3-diynes has been developed for the synthesis 3-alkynylated isoquinolines engaging 2-aminopyridine as a traceless bidentate directing group. The strategy successfully extended 3,3′-biisoquinoline moieties via both one-pot well sequential approaches. utilization group with an inexpensive earth-abundant cobalt-catalyst under operationally simple reaction conditions makes present transformation more valuable appealing.

Language: Английский

Citations

47
A Highly Efficient Dimeric Manganese‐Catalyzed Selective Hydroarylation of Internal Alkynes DOI

Yubo Pang,

Gengtu Liu,

Congcong Huang

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(31), P. 12789 - 12794

Published: April 24, 2020

We have developed a general and site-predictable manganese-catalyzed hydroarylation of internal alkynes in the presence water, under an air atmosphere without involvement ligand. The unique catalytic feature this reaction is highlighted by comparison with other widely used transition metal catalysts including palladium, rhodium, nickel, or copper. simple operation, high efficiency excellent functional group compatibility make protocol practical for more than 90 structurally diverse alkynes, overcoming influence both electronic steric effect alkynes. Its exclusive regio- chemoselectivity originates from reactivity manganese-based catalyst towards inherent double controlled strategy sterically hindered propargyl alcohols installing external directing groups. synthetic robustness practicality been illustrated concise synthesis bervastatin, hypolipidemic drug, late-stage modification complex precise regioselectivity.

Language: Английский

Citations

45