3d Transition Metals for C–H Activation

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2192 - 2452

Published: Nov. 27, 2018

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these functionalizations required precious 4d or 5d transition metal catalysts. Given cost-effective sustainable nature earth-abundant first row metals, development less toxic, inexpensive 3d catalysts gained considerable recent momentum a significantly more environmentally-benign economically-attractive alternative. Herein, we provide comprehensive overview on until summer 2018.

Language: Английский

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Highly Selective Synthesis of 1,3-Enynes, Pyrroles, and Furans by Manganese(I)-Catalyzed C–H Activation

ACS Catalysis, Journal Year: 2019, Volume and Issue: 10(1), P. 197 - 202

Published: Nov. 21, 2019

A highly selective Mn(I)-catalyzed alkenylation of arenes and heteroarenes with 1,3-diynes is described. The reported transformation overcomes regio-, chemo-, stereoselectivity challenges associated the use these coupling partners. Both symmetrical unsymmetrical diynes can be applied in this protocol, affording single isomers not only synthesis 1,3-enynes but also one-step preparation pyrroles furans. This simple strategy features wide functional group tolerance, good reproducibility, preparative scale utility. manganese catalyst plays a crucial role C–H activation enabling high selectivity previously challenging internal alkynes. Furthermore, synthetic value method highlighted by diverse postsynthesis functionalizations final products.

Language: Английский

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Propargylic Alcohols as Coupling Partners in Transition‐Metal‐Catalyzed Arene C−H Activation

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(23), P. 5238 - 5256

Published: Sept. 21, 2020

Abstract Transition‐metal‐catalyzed site selective arene C−H bond activation concomitant functionalization with various coupling partners gain magnificent attraction in synthetic organic chemistry as complementary to traditional transformations. Mechanistically, these approaches involve directing group assisted concerted metalation‐deprotonation (CMD), migratory insertion, and reductive elimination sequences. In this realm, diverse categories of were employed buddies. Particularly alkynes enormous attention annulating agents. These units coordinates metalcycle through π‐interaction produce annulation outcomes a straightforward manner. Very recently, propargylic alcohols appointed valuable archetypes armoury, they have shown regio‐ chemoselective insertion into primary species via hydroxy chelation. The influential regioselectivity was drawn by dual coordination metal complexes the pendent hydroxyl group. review, we focused on annulations arenes alcohols, which afford intricate cycles well complex acyclic motifs trouble‐free We categorized transformations based number atoms involved along some addition reactions. anticipate pave way towards enhanced endeavours for discovering novel reaction avenues. magnified image

Language: Английский

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Stereocontrolled transformations of cyclohexadienone derivatives to access stereochemically rich and natural product-inspired architectures

Organic & Biomolecular Chemistry, Journal Year: 2020, Volume and Issue: 18(42), P. 8526 - 8571

Published: Jan. 1, 2020

Multi-divergent transformations of cyclohexadienone derivatives for the synthesis stereoenriched and complex architectures.

Language: Английский

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

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

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

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

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Rh(III)-Catalyzed Double C–H Functionalization of Indoles with Cyclopropenones via Sequential C–H/C–C/C–H Bond Activation

Organic Letters, Journal Year: 2023, Volume and Issue: 25(21), P. 3922 - 3926

Published: May 18, 2023

An unprecedented Rh(III)-catalyzed double C-H functionalization of indoles with cyclopropenones via sequential C-H/C-C/C-H bond activation has been developed. This procedure represents the first example for assembling cyclopenta[b]indoles utilizing as 3C synthons. powerful approach shows excellent chemo- and regioselectivity, wide functional group tolerance, good reaction yields.

Language: Английский

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Polycyclic Pyrazoles from Alkynyl Cyclohexadienones and Nonstabilized Diazoalkanes via [3 + 2]-Cycloaddition/[1,5]-Sigmatropic Rearrangement/Aza-Michael Reaction Cascade

Organic Letters, Journal Year: 2024, Volume and Issue: 26(4), P. 839 - 844

Published: Jan. 22, 2024

An efficient method for the stereoselective synthesis of "all center substituted" polycyclic pyrazoles from alkynyl cyclohexa-2,5-dienones and nonstabilized diazoalkanes via sequential [3 + 2]-cycloaddition/[1,5]-sigmatropic rearrangement aza-Michael reactions is reported. The developed process highly regioselective stereoselective. It employs a wide substrate scope to furnish structurally diverse linear bridged [4.4.n.0] ring-fused in moderate good yields. One-pot gram-scale syntheses synthetic transformations have also been showcased.

Language: Английский

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Rhodium(III)-Catalyzed C–H Alkenylation/Directing Group Migration for the Regio- and Stereoselective Synthesis of Tetrasubstituted Alkenes

Organic Letters, Journal Year: 2020, Volume and Issue: 22(23), P. 9163 - 9168

Published: Nov. 16, 2020

An efficient Rh(III)-catalyzed C–H alkenylation/directing group migration cascade between indoles and alkynes for the assembly of tetrasubstituted alkenes is reported. The carbamoyl directing migrates to carbon alkene moiety products through rare Rh-catalyzed C–N bond cleavage after alkenylation step thus acts as an internal amidation reagent. This protocol shows broad substrate scope, excellent regio/stereoselectivity, good yields.

Language: Английский

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Directed Cobalt-Catalyzed anti-Markovnikov Hydroalkylation of Unactivated Alkenes Enabled by “Co–H” Catalysis

Organic Letters, Journal Year: 2020, Volume and Issue: 22(11), P. 4333 - 4338

Published: May 13, 2020

The earth-abundant cobalt-catalyzed anti-Markovnikov hydroalkylation of unactivated alkenes with oxime esters was achieved by introducing an 8-aminoquinoline directing group on the alkenes. catalytic system, consisting commercially available Co(acac)3 and PhMeSiH2, enables construction unfunctionalized C(sp3)-C(sp3) bonds features exclusive selectivity, good functional tolerance, avoidance extra ligand, oxidant, or base. Mechanistic insight into this new system indicates involvement both alkyl radical cobalt hydride intermediates.

Language: Английский

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