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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Decarboxylative reactions with and without light – a comparison

Green Chemistry, Journal Year: 2017, Volume and Issue: 20(2), P. 323 - 361

Published: Nov. 13, 2017

Carboxylic acids have gained more and importance as versatile renewable starting materials for the formation of platform molecules or high-value chemicals.

Language: Английский

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Strategic evolution in transition metal-catalyzed directed C–H bond activation and future directions

Coordination Chemistry Reviews, Journal Year: 2020, Volume and Issue: 431, P. 213683 - 213683

Published: Dec. 9, 2020

Language: Английский

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Controlled functionalization ofo-carboraneviatransition metal catalyzed B–H activation

Chemical Society Reviews, Journal Year: 2019, Volume and Issue: 48(13), P. 3660 - 3673

Published: Jan. 1, 2019

This review summarizes recent advances in transition metal catalyzed vertex-specific BH functionalization ofo-carborane for controlled synthesis of its derivatives.

Language: Английский

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A Unified Approach to Decarboxylative Halogenation of (Hetero)aryl Carboxylic Acids

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(18), P. 8296 - 8305

Published: April 29, 2022

Aryl halides are a fundamental motif in synthetic chemistry, playing critical role metal-mediated cross-coupling reactions and serving as important scaffolds drug discovery. Although thermal decarboxylative functionalization of aryl carboxylic acids has been extensively explored, the scope existing halodecarboxylation methods remains limited, there currently exists no unified strategy that provides access to any type halide from an acid precursor. Herein, we report general catalytic method for direct halogenation (hetero)aryl via ligand-to-metal charge transfer. This accommodates exceptionally broad substrates. We leverage radical intermediate toward divergent pathways: (1) atom transfer bromo- or iodo(hetero)arenes (2) capture by copper subsequent reductive elimination generate chloro- fluoro(hetero)arenes. The proposed mechanism is supported through array spectroscopic studies.

Language: Английский

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C4–H indole functionalisation: precedent and prospects

Chemical Science, Journal Year: 2018, Volume and Issue: 9(18), P. 4203 - 4216

Published: Jan. 1, 2018

This Perspective article traces the evolution of modern approaches to functionalise indole C4–H bond.

Language: Английский

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The 2‐Pyridyl Problem: Challenging Nucleophiles in Cross‐Coupling Arylations

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(20), P. 11068 - 11091

Published: Sept. 17, 2020

Azine-containing biaryls are ubiquitous scaffolds in many areas of chemistry, and efficient methods for their synthesis continually desired. Pyridine rings prominent amongst these motifs. Transition-metal-catalysed cross-coupling reactions have been widely used functionalisation as they often provide a swift tuneable route to related biaryl scaffolds. However, 2-pyridine organometallics capricious coupling partners 2-pyridyl boron reagents particular notorious instability poor reactivity Suzuki-Miyaura reactions. The pyridine-containing is therefore limited, the formation unsymmetrical 2,2'-bis-pyridines scarce. This Review focuses on developed challenging nucleophiles with (hetero)aryl electrophiles, ranges from traditional processes alternative nucleophilic novel main group approaches.

Language: Английский

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Cobalt‐Catalyzed Coupling of Benzoic Acid C−H Bonds with Alkynes, Styrenes, and 1,3‐Dienes

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(6), P. 1688 - 1691

Published: Jan. 10, 2018

Abstract A method for cobalt‐catalyzed, carboxylate‐directed functionalization of arene C−H bonds is reported. Alkynes, styrenes, and 1,3‐dienes can be coupled with benzoic acids to provide cyclic products in good yields. The reactions proceed the presence a cobalt(II) hexafluoroacetylacetonate catalyst, (TMS) 2 NH base, Ce(SO 4 ) cooxidant, oxygen oxidant.

Language: Английский

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Transition-Metal-Free Decarboxylative Iodination: New Routes for Decarboxylative Oxidative Cross-Couplings

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(33), P. 11527 - 11536

Published: July 23, 2017

Constructing products of high synthetic value from inexpensive and abundant starting materials is great importance. Aryl iodides are essential building blocks for the synthesis functional molecules, efficient methods their chemical feedstocks highly sought after. Here we report a low-cost decarboxylative iodination that occurs simply readily available benzoic acids I2. The reaction scalable scope robustness thoroughly examined. Mechanistic studies suggest this does not proceed via radical mechanism, which in contrast to classical Hunsdiecker-type halogenations. In addition, DFT allow comparisons be made between our procedure current transition-metal-catalyzed decarboxylations. utility demonstrated its application oxidative cross-couplings aromatics decarboxylative/C-H or double activations use I2 as terminal oxidant. This strategy allows preparation biaryls previously inaccessible holds other advantages over existing couplings, stoichiometric transition metals avoided.

Language: Английский

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Ruthenium(II)-Catalyzed Hydroarylation of Maleimides Using Carboxylic Acids as a Traceless Directing Group

Organic Letters, Journal Year: 2017, Volume and Issue: 19(15), P. 4138 - 4141

Published: July 20, 2017

An efficient Ru(II)-catalyzed hydroarylation of maleimides with ready-stock aryl carboxylic acids has been developed based on weak carboxylate-directed ortho-C–H alkylation and concomitant decarboxylation processes, fabricating 3-aryl succinimides, a recurrent scaffold in drug molecules, high yields (up to 97%). The protocol features operational simplicity, avoids the need for precious metal additives/oxidants, offers broad substrate scope formal meta- para-selectivities. It represents first example direct arylation unbiased benzoic acids.

Language: Английский

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