Late‐Stage Functionalization of Arylacetic Acids by Photoredox‐Catalyzed Decarboxylative Carbon–Heteroatom Bond Formation

Sakakibara, Yota; Ito, Eri; Fukushima, Tomohiro; Murakami, Kei; Itami, Kenichiro

doi:10.1002/chem.201802143

Cited by 40 publications

(24 citation statements)

References 47 publications

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“…The same group's subsequent study revealed that the same methodology can also be extended for construction of carbon–nitrogen and carbon–oxygen bonds ( Figure 11B ) (Sakakibara et al, 2018b ). Under the activation of IBB, arylacetic acids were directly converted into nitrogen, oxygen, or chlorine functionalities.…”

Section: Hirs Act As Oxidants For Substrate Activationmentioning

confidence: 99%

Recent Synthetic Applications of the Hypervalent Iodine(III) Reagents in Visible-Light-Induced Photoredox Catalysis

2020

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The synergistic combination of visible-light-induced photoredox catalysis with hypervalent iodine(III) reagents (HIRs) represents a particularly important achievement in the field of hypervalent iodine chemistry, and numerous notable organic transformations were achieved in a mild and environmentally benign fashion. This account intends to summarize recent synthetic applications of HIRs in visible-light-induced photoredox catalysis, and they are organized in terms of the photochemical roles of HIRs played in reactions.

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Section: Hirs Act As Oxidants For Substrate Activationmentioning

confidence: 99%

Recent Synthetic Applications of the Hypervalent Iodine(III) Reagents in Visible-Light-Induced Photoredox Catalysis

2020

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“…The chloromethyl radical generation by photoredox catalysis is a useful strategy for cyclopropanation [58]. Most photoredox catalyzed, decarboxylative generations of carbon-centered radicals are based on the formation of "stabilized" α-amino [59][60][61][62][63][64][65] or benzyl [66][67][68][69][70] radical species. However, the generation of unstabilized alkyl radical species is also known [71][72][73][74].…”

Section: Resultsmentioning

confidence: 99%

Visible-light-induced addition of carboxymethanide to styrene from monochloroacetic acid

Vliet¹,

Leeuwen²,

Brouwer³

et al. 2020

Beilstein J. Org. Chem.

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Where monochloroacetic acid is widely used as a starting material for the synthesis of relevant groups of compounds, many of these synthetic procedures are based on nucleophilic substitution of the carbon chlorine bond. Oxidative or reductive activation of monochloroacetic acid results in radical intermediates, leading to reactivity different from the traditional reactivity of this compound. Here, we investigated the possibility of applying monochloroacetic acid as a substrate for photoredox catalysis with styrene to directly produce γ-phenyl-γ-butyrolactone. Instead of using nucleophilic substitution, we cleaved the carbon chlorine bond by single-electron reduction, creating a radical species. We observed that the reaction works best in nonpolar solvents. The reaction does not go to full conversion, but selectively forms γ-phenyl-γ-butyrolactone and 4-chloro-4-phenylbutanoic acid. Over time the catalyst precipitates from solution (perhaps in a decomposed form in case of fac-[Ir(ppy)3]), which was proven by mass spectrometry and EPR spectroscopy for one of the catalysts (N,N-5,10-di(2-naphthalene)-5,10-dihydrophenazine) used in this work. The generation of HCl resulting from lactone formation could be an additional problem for organometallic photoredox catalysts used in this reaction. In an attempt to trap one of the radical intermediates with TEMPO, we observed a compound indicating the generation of a chloromethyl radical.

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“…In 2018, the Itami group found arylacetic acids could be converted into coupling products 5.1 by a photoredox‐catalyzed carbon‐heteroatom bond formation (Eq. 5–1).…”

Section: Decarboxylationmentioning

confidence: 99%

Arylacetic Acids in Organic Synthesis

et al. 2019

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Arylacetic acids are widely used in organic reactions and their recent advances are summarized in six categories according to their triggered pathways: (1) the acid as directing group in ortho-or meta-CÀ H activation; (2) decarboxylation; (3) deprotonation; (4) nucleophilic methylenes; (5) nucleophilic acids; (6) electrophilic acids. Reactions with alkenes, alkynes, aldehydes, amines, water, Grignard reagents, silanes and so forth are discussed. We hope this Minireview will promote future research in this area. Recently, the Zeng group [3g] reported a weakly coordinationassisted alkynylation of arylacetic acids with iridium catalysis under air atmosphere (Eq. 2-2). It was supported the sixmembered ring cycloiridiated 2.5 acted as the key intermediate. The alkynylation of indole, thiophene, pyrrole, and benzo[b] thiophene afforded better yields than phenylacetic acids. The acid moiety could also participated in the intramolecular ortho-CÀ H activation, which was developed by the Shi group to obtain lactonization 2.6 (Eq. 2-3) (Scheme 2). Meta-CÀ H ArylationThe study of Yu group [3e] in 2017 revealed a successful control of meta selectivity 3.1 of arylation from aryl iodides (Eq. 3-1). The use of mono-protected 3-amino-2-hydroxypyridine (as ligand) and 2-carbomethoxynorbornene (NBE-CO 2 Me) were crucial. In the absence of NBE-CO 2 Me, only ortho-arylated product was obtained. This method was still efficient in a gramsale (Scheme 3). Decarboxylation Decarboxylative CouplingAs shown in Scheme 4, the decarboxylation could generate benzyl radicals 4.1. Then, direct couplings of 4.1 with diverse [ + ] These authors contributed equally. Scheme 1. Six categories based on triggered mechanism. 2 3 4 5 6 7 8 . Passerini Three-Component ReactionThe Passerini reaction was the oldest multicomponent reaction (MCR) [37d] in which isocyanides, carboxylic acids and aldehydes were used. It was powerful for the rapid construction of complex molecules. The tactic to expand the scope of Passerini reaction was to use surrogates of the carbonyl partners. As described in Scheme 51, syn-chlorooximes, [37b] diazoketones, [37c] alcohols, [37d,e] azirines [37f] and isatins [37g] could be employed instead of aryl or alkyl aldehydes [37a] (Scheme 51). Besides, in 2018, Zhang and co-workers [37] have firstly reported asymmetric phosphoric acid-catalyzed four-component Ugi reaction, which Scheme 45. BTM-catalyzed cycloaddition. Scheme 46. HBTM-catalyzed cycloaddition. Scheme 47. TFA-catalyzed reaction. Scheme 48. Friedel-Crafts triggered tandem reactions. Scheme 49. C-acylation of 1,3-diones. Scheme 50. C-acylation of 1,3-indandiones.

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Late‐Stage Functionalization of Arylacetic Acids by Photoredox‐Catalyzed Decarboxylative Carbon–Heteroatom Bond Formation

Cited by 40 publications

References 47 publications

Recent Synthetic Applications of the Hypervalent Iodine(III) Reagents in Visible-Light-Induced Photoredox Catalysis

Recent Synthetic Applications of the Hypervalent Iodine(III) Reagents in Visible-Light-Induced Photoredox Catalysis

Visible-light-induced addition of carboxymethanide to styrene from monochloroacetic acid

Arylacetic Acids in Organic Synthesis

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