Recent Advances in External-Directing-Group-Free C–H Functionalization of Carboxylic Acids without Decarboxylation

ACS Catalysis, Год журнала: 2021, Номер 11(7), С. 4205 - 4229

Опубликована: Март 19, 2021

The selective functionalization of C–H bonds is an extremely important topic in present-day organic synthesis, as it utilizes the most abundant portion a molecule tool for synthetic manipulations. Despite great progress over past decade, major limitation remains use equivalent amount directing group to generate product. utilization native carboxylate same purpose has come up better alternative perform activation, no exogenous required reaction. In this Perspective, we intend provide broader picture transformations that have been carried out by assistance from and could be applied routinely synthesis complex molecules. intact carboxylic substrate further transformed into different functional moieties, which increases diversity such reactions. Extensive coverage carboxylate-aided functionalizations molecules without decarboxylation expected make Perspective unique beneficial researchers academia industry.

Язык: Английский

---

Site-Selective Cross-Coupling of Polyhalogenated Arenes and Heteroarenes with Identical Halogen Groups

Chemical Reviews, Год журнала: 2021, Номер 122(11), С. 10126 - 10169

Опубликована: Авг. 17, 2021

Methods to functionalize arenes and heteroarenes in a site-selective manner are highly sought after for rapidly constructing value-added molecules of medicinal, agrochemical, materials interest. One effective approach is the cross-coupling polyhalogenated bearing multiple, but identical, halogen groups. Such reactions have proven be incredibly functionalization. However, they also present formidable challenges due inherent similarities reactivities substituents. In this Review, we discuss strategies cross-couplings identical halogens, beginning first with an overview reaction types that more traditional nature, such as electronically, sterically, directing-group-controlled processes. Following these examples description emerging strategies, which includes ligand- additive/solvent-controlled well photochemically initiated

Язык: Английский

---

Traceless directing groups: a novel strategy in regiodivergent C–H functionalization

Chemical Communications, Год журнала: 2020, Номер 56(83), С. 12479 - 12521

Опубликована: Янв. 1, 2020

The use of functional groups as internal ligands for assisting C-H functionalization, termed the chelation assisted strategy, is emerging one most powerful tools construction C-C and C-X bonds from inert bonds. However, there are various directing which cannot be either removed after functionalization or require some additional steps reagents their removal, thereby limiting scope structural diversity products, step atom economy system. These limitations overcome by traceless group (TDG) strategy wherein substrate removal can carried out in a pot fashion. Traceless serve ideal with high degree reactivity selectivity without any requirement removal. present review overviews such carboxylic acids, aldehydes, N-oxides, nitrones, N-nitroso amines, amides, sulfoxonium ylides silicon tethered transition metal catalyzed reactions last decade.

Язык: Английский

---

Wonderful fusion of organofluorine chemistry and decarboxylation strategy

Chemical Society Reviews, Год журнала: 2021, Номер 50(10), С. 6094 - 6151

Опубликована: Янв. 1, 2021

Decarboxylation strategy has been emerging as a powerful tool for the synthesis of fluorine-containing organic compounds that play important roles in various fields such pharmaceuticals, agrochemicals, and materials science. Considerable progress decarboxylation made over past decade towards construction diverse valuable fluorinated fine chemicals which part can be brought two ways. The first way is described reaction non-fluorinated carboxylic acids (and their derivatives) with fluorinating reagents, well building blocks. second dedicated to exploration use decarboxylative transformations. This review aims provide comprehensive summary development applications radical, nucleophilic cross-coupling strategies organofluorine chemistry.

Язык: Английский

---

Regiospecific ortho‐C−H Allylation of Benzoic Acids

Angewandte Chemie International Edition, Год журнала: 2018, Номер 57(44), С. 14580 - 14584

Опубликована: Фев. 7, 2018

A carboxylate-directed ortho-C-H functionalization has been developed and it allows the regiospecific introduction of allyl residues to benzoic acids. In presence a [Ru(p-cymene)Cl2 ]2 K3 PO4 , acids react with acetates at only 50 °C give corresponding ortho-allylbenzoic The protocol is generally applicable both electron-rich electron-poor in combination linear branched acetates. products can be further functionalized situ, for example, by double-bond migration, lactonization, or decarboxylation.

Язык: Английский

---

Single Electron Activation of Aryl Carboxylic Acids

iScience, Год журнала: 2020, Номер 23(7), С. 101266 - 101266

Опубликована: Июнь 12, 2020

Aryl carboxylic acids are stable and readily available in great structural diversity both from natural well-established synthetic procedures, which make them promising starting materials organic synthesis. The conversion of benzoic into high-value molecules is importance have gained much interest chemists. recent development single-electron (1e−) activation strategy has been esteemed as a complementary method for the transformation acids. In this context, carboxylate groups can be selectively transferred reactive aryl radical, acyl radical by electrocatalysis, photocatalysis, or presence some SET oxidants. Based on these species, remarkable advancements achieved rapid formation various chemical bonds over past 10 years. review, we summarize advances single electron acids, with an emphasis reaction scope, catalytic system, limitation, underlying mechanism.

Язык: Английский

---

A Guide to Directing Group Removal: 8‐Aminoquinoline

Chemistry - A European Journal, Год журнала: 2021, Номер 27(33), С. 8411 - 8436

Опубликована: Фев. 10, 2021

The use of directing groups allows high levels selectivity to be achieved in transition metal-catalyzed transformations. Efficient removal these auxiliaries after successful functionalization, however, can very challenging. This review provides a critical overview strategies used for Daugulis' 8-aminoquinoline (2005-2020), one the most widely N,N-bidentate groups. limitations are discussed and alternative approaches suggested challenging substrates. Our aim is provide comprehensive end-users' guide chemists academia industry who want harness synthetic power groups-and able remove them from their final products.

Язык: Английский

---

Pd-catalysed C–H functionalisation of free carboxylic acids

Chemical Science, Год журнала: 2022, Номер 13(9), С. 2551 - 2573

Опубликована: Янв. 1, 2022

Pd-catalysed C–H functionalisation of free carboxylic acids has drawn significant attention over the last few years due to predominance acid moieties in pharmaceuticals and agrochemicals.

Язык: Английский

---

Chemoselective Decarboxylative Protonation Enabled by Cooperative Earth‐Abundant Element Catalysis

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(3)

Опубликована: Ноя. 9, 2022

Decarboxylative protonation is a general deletion tactic to replace polar carboxylic acid groups with hydrogen or its isotope. Current methods rely on the pre-activation of acids, non-sustainable sources, and/or expensive/highly oxidizing photocatalysts, presenting challenges their wide adoption. Here we show that cooperative iron/thiol catalyst system can readily achieve this transformation, hydrodecarboxylating range activated and unactivated acids overcoming scope limitations in previous direct methods. The reaction scaled batch configuration be directly performed deuterated solvent afford high yields d-incorporated products excellent isotope incorporation efficiency; characteristics not attainable photocatalyzed approaches. Preliminary mechanistic studies indicate radical mechanism kinetic results (KIE=1) are consistent light-limited reaction.

Язык: Английский

---

Efficient biobased carboxylic acids synthesis by synergistic electrocatalysis of multi-active sites on bimetallic Cu-Co oxide/oxyhydroxide

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 331, С. 122709 - 122709

Опубликована: Март 31, 2023

Язык: Английский

---