Decarboxylative Hydroxylation of Benzoic Acids

Su, Wanqi; Xu, Peng; Ritter, Tobias

doi:10.1002/ange.202108971

Cited by 10 publications

(1 citation statement)

References 78 publications

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“…Ritter and co-workers have described protocols for the fluorodecarboxylation of aryl carboxylic acids via copper(II)−LMCT as well as the formation of the homocoupled benzoic ester product to access phenols after in situ hydrolysis. 59,60 In summary, our novel approach to photocatalytic coppercatalyzed decarboxylative C(sp 2 )−X bond formation allows facile access to a diversity of fundamentally useful arene products and has been efficiently applied in the setting of complex, pharmaceutically relevant molecules. We envision that this unified strategy will provide a valuable synthetic toolbox for academic and industrial chemists alike, and we are working to expand this platform to include additional useful transformations.…”

Section: Decarboxylative C(sp 2 )−X Bond-formation Reactionsmentioning

confidence: 99%

Carboxylic Acids as Adaptive Functional Groups in Metallaphotoredox Catalysis

et al. 2022

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Conspectus The development of palladium-catalyzed cross-coupling methods for the activation of C(sp2)–Br bonds facilitated access to arene-rich molecules, enabling a concomitant increase in the prevalence of this structural motif in drug molecules in recent decades. Today, there is a growing appreciation of the value of incorporating saturated C(sp3)-rich scaffolds into pharmaceutically active molecules as a means to achieve improved solubility and physiological stability, providing the impetus to develop new coupling strategies to access these challenging motifs in the most straightforward way possible. As an alternative to classical two-electron chemistry, redox chemistry can enable access to elusive transformations, most recently, by interfacing abundant first-row transition-metal catalysis with photoredox catalysis. As such, the functionalization of ubiquitous and versatile functional handles such as (aliphatic) carboxylic acids via metallaphotoredox catalysis has emerged as a valuable field of research over the past eight years. In this Account, we will outline recent progress in the development of methodologies that employ aliphatic and (hetero)aromatic carboxylic acids as adaptive functional groups. Whereas recent decarboxylative functionalization methodologies often necessitate preactivated aliphatic carboxylic acids in the form of redox-active esters or as ligands for hypervalent iodine reagents, methods that enable the direct use of the native carboxylic acid functionality are highly desired and have been accomplished through metallaphotoredox protocols. As such, we found that bench-stable aliphatic carboxylic acids can undergo diverse transformations, such as alkylation, arylation, amination, and trifluoromethylation, by leveraging metallaphotoredox catalysis with prevalent first-row transition metals such as nickel and copper. Likewise, abundant aryl carboxylic acids are now able to undergo halogenation and borylation, enabling new entry points for traditional, primarily palladium- or copper-catalyzed cross-coupling strategies. Given the breadth of the functional group tolerance of the employed reaction conditions, the late-stage functionalization of abundant carboxylic acids toward desired targets has become a standard tool in reaction design, enabling the synthesis of various diversified drug molecules. The rapid rise of this field has positively inspired pharmaceutical discovery and will be further accelerated by novel reaction development. The achievement of generality through reaction optimization campaigns allows for future breakthroughs that can render protocols more reliable and applicable for industry. This article is intended to highlight, in particular, (i) the employment of aliphatic and (hetero)aryl carboxylic acids as powerful late-stage adaptive functional handles in drug discovery and (ii) the need for the further development of still-elusive and selective transformations. We strongly believe that access to native functionalities such as carboxylic acids as adaptive handles will...

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Section: Decarboxylative C(sp 2 )−X Bond-formation Reactionsmentioning

confidence: 99%

Carboxylic Acids as Adaptive Functional Groups in Metallaphotoredox Catalysis

et al. 2022

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Photoinduced Ligand‐to‐Metal Charge Transfer of Carboxylates: Decarboxylative Functionalizations, Lactonizations, and Rearrangements

et al. 2022

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In the quest for sustainable processes, the selection of resources and catalysts is of central importance. Carboxylic acids, which are abundant, stable and ideally biobased feedstocks, can be considered as attractive platforms towards a range of functionalized molecules. A recent resurgence of photoinduced ligand‐to‐metal charge transfer (LMCT) of carboxylates led to tremendous developments in the field of earth‐abundant metal mediated, visible‐light induced (non)‐decarboxylative transformations of carboxylic acids. These reactions combine the use of available starting materials, low‐consuming energy source and abundant catalysts. Besides these undeniable advantages, they also provide mild, highly selective and innovative conditions towards complex molecule functionalization. The objective of this review is to give an overview of the recent advances in LMCT of carboxylates with a special focus on mechanistic aspects of these transformations.

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Meerwein‐type Bromoarylation with Arylthianthrenium Salts

Cai

Ritter

2022

Angewandte Chemie

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Herein, we report a photocatalyzed Meerwein‐type bromoarylation of alkenes with stable arylthianthrenium salts, formed by site‐selective C−H thianthrenation. This protocol can be applied to late‐stage functionalization of a variety of biomolecules that are difficult to access by other aryl coupling reagents. Halogen introduction allows for a variety of follow‐up transformations, affording numerous biologically active skeletons.

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Decarboxylative Hydroxylation of Benzoic Acids

Cited by 10 publications

References 78 publications

Carboxylic Acids as Adaptive Functional Groups in Metallaphotoredox Catalysis

Carboxylic Acids as Adaptive Functional Groups in Metallaphotoredox Catalysis

Photoinduced Ligand‐to‐Metal Charge Transfer of Carboxylates: Decarboxylative Functionalizations, Lactonizations, and Rearrangements

Meerwein‐type Bromoarylation with Arylthianthrenium Salts

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