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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A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(17), P. 6603 - 6743

Published: Jan. 1, 2018

The present review is devoted to summarizing the recent advances (2015-2017) in field of metal-catalysed group-directed C-H functionalisation. In order clearly showcase molecular diversity that can now be accessed by means directed functionalisation, whole organized following directing groups installed on a substrate. Its aim comprehensive reference work, where specific group easily found, together with transformations which have been carried out it. Hence, primary format this schemes accompanied concise explanatory text, are ordered sections according their chemical structure. feature typical substrates used, products obtained as well required reaction conditions. Importantly, each example commented respect most important positive features and drawbacks, aspects such selectivity, substrate scope, conditions, removal, greenness. targeted readership both experts functionalisation chemistry (to provide overview progress made last years) and, even more so, all organic chemists who want introduce way thinking for design straightforward, efficient step-economic synthetic routes towards molecules interest them. Accordingly, should particular also scientists from industrial R&D sector. overall goal promote application reactions outside research dedicated method development establishing it valuable archetype contemporary R&D, comparable role cross-coupling play date.

Language: Английский

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Electrochemical Oxidative Cross-Coupling with Hydrogen Evolution Reactions

Accounts of Chemical Research, Journal Year: 2019, Volume and Issue: 52(12), P. 3309 - 3324

Published: Nov. 27, 2019

Oxidative cross-coupling has proved to be one of the most straightforward strategies for forming carbon-carbon and carbon-heteroatom bonds from easily available precursors. Over past two decades, tremendous efforts have been devoted in this field significant advances achieved. However, order remove surplus electrons substrates chemical formation, stoichiometric oxidants are usually needed. Along with development modern sustainable chemistry, considerable perform oxidative reactions under external-oxidant-free conditions. Electrochemical synthesis is a powerful environmentally benign approach, which can not only achieve cross-couplings conditions, but also release valuable hydrogen gas during bond formation. Recently, electrochemical evolution significantly explored. This Account presents our recent toward reactions. (1) We explored thiols/thiophenols arenes, heteroarenes, alkenes C-S (2) Using strategy C-H/N-H evolution, we successfully realized C-H amination phenols, anilines, imidazopyridines, even ethers. (3) Employing halide salts as green halogenating reagents, developed clean halogenation protocol oxidation To address limitation that reaction had carry out aqueous solvent, an alternative method uses CBr4, CHBr3, CH2Br2, CCl3Br, CCl4 reagents mixture acetonitrile methanol cosolvent. (4) approach constructing C-O well-developed manner. (5) Under mild C(sp2)-H C(sp3)-H phosphonylation modest high yields. (6) achieved S-H/S-H By anodic instead oxidants, overoxidation thiols thiophenols was well avoided. (7) The methods structurally diverse heterocyclic compounds were via annulations. (8) applied difunctionalization multiple step, such C-S/C-O bonds, C-S/C-N C-Se/C-O C-Se/C-N bonds. hope studies will stimulate research interest chemists pave way discovery more

Language: Английский

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(Pentamethylcyclopentadienyl)cobalt(III)‐Catalyzed C–H Bond Functionalization: From Discovery to Unique Reactivity and Selectivity

Advanced Synthesis & Catalysis, Journal Year: 2017, Volume and Issue: 359(8), P. 1245 - 1262

Published: March 16, 2017

Abstract High‐valent (pentamethylcyclopentadienyl)cobalt(III) [Cp*Co(III)] catalysts were found as inexpensive alternatives to (pentamethylcyclopentadienyl)rhodium(III) [Cp*Rh(III)] in the field of C—H bond functionalization, and applied a variety transformations. In this review, after discovery early examples Cp*Co(III)‐catalyzed functionalization are summarized, unique reactivity selectivity Cp*Co(III) differences between cobalt rhodium catalysis intensively discussed. Such assumed be caused by lower electronegativity, hard nature, smaller ionic radius cobalt. magnified image

Language: Английский

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Palladium-Catalyzed Cross-Coupling Reactions: A Powerful Tool for the Synthesis of Agrochemicals

Journal of Agricultural and Food Chemistry, Journal Year: 2018, Volume and Issue: 66(34), P. 8914 - 8934

Published: July 31, 2018

Pd-catalyzed cross-coupling reactions have become essential tools for the construction of carbon–carbon and carbon–heteroatom bonds. Over last three decades, great efforts been made with chemistry in discovery, development, commercialization innovative new pharmaceuticals agrochemicals (mainly herbicides, fungicides, insecticides). In view growing interest both modern crop protection chemistry, this review gives a comprehensive overview successful applications various methodologies, which implemented as key steps synthesis (on R&D pilot-plant scales) such Heck, Suzuki, Sonogashira, Stille, Negishi reactions, well decarboxylative, carbonylative, α-arylative, carbon–nitrogen bond bond-forming reactions. Some perspectives challenges these catalytic coupling processes discovery are briefly discussed final section. The examples chosen demonstrate that approaches open-up new, low-cost, more efficient industrial routes to existing agrochemicals, methods also capability lead generation pesticides novel modes action sustainable protection.

Language: Английский

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Electrochemical Cobalt-Catalyzed C–H Oxygenation at Room Temperature

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(51), P. 18452 - 18455

Published: Nov. 18, 2017

Electrochemical cobalt-catalyzed C–H functionalizations were achieved in terms of oxygenation under mild conditions at 23 °C. The robust electrochemical functionalization was characterized by ample substrate scope, whereas mechanistic studies provided support for a facile cleavage. proved viable on arenes and alkenes with excellent levels positional diastereo-selectivity, avoiding the use stoichiometric silver(I) oxidants ambient conditions.

Language: Английский

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Electrocatalytic Oxidant‐Free Dehydrogenative C−H/S−H Cross‐Coupling

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(11), P. 3009 - 3013

Published: Feb. 8, 2017

An environmentally friendly electrocatalytic protocol has been developed for dehydrogenative C-H/S-H cross-coupling. This method enabled C-S bond formation under catalyst- and oxidant-free conditions. Under undivided electrolysis conditions, various aryl/heteroaryl thiols electron-rich arenes afforded the bond-formation products in 24-99 % yield. A preliminary mechanistic study indicated that generation of aryl radical cation intermediates is key to success this transformation.

Language: Английский

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C–H functionalization by high-valent Cp*Co(iii) catalysis

Chemical Communications, Journal Year: 2017, Volume and Issue: 53(22), P. 3165 - 3180

Published: Jan. 1, 2017

Significant progress has been accomplished in directed C–H functionalization through the use of earth-abundant and inexpensive first-row transition metals.

Language: Английский

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Transition-Metal-Catalyzed C–S, C–Se, and C–Te Bond Formations via Cross-Coupling and Atom-Economic Addition Reactions. Achievements and Challenges

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(21), P. 16110 - 16293

Published: Sept. 16, 2022

In the present review, we discuss recent progress in field of C–Z bond formation reactions (Z = S, Se, Te) catalyzed by transition metals. Two complementary methodologies are considered─catalytic cross-coupling and catalytic addition reactions. The development advanced systems is aimed at improved catalyst efficiency, reduced loading, better cost environmental concerns, higher selectivity yields. important rise research efforts sustainability green chemistry areas critically assessed. paramount role mechanistic studies a new generation addressed, key achievements, problems, challenges summarized for this field.

Language: Английский

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Recent advances in iodine mediated electrochemical oxidative cross-coupling

Organic & Biomolecular Chemistry, Journal Year: 2018, Volume and Issue: 16(14), P. 2375 - 2387

Published: Jan. 1, 2018

This review article gives an overview of the recent development iodine mediated electrochemical oxidative coupling reactions.

Language: Английский

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