Photocatalytic One-Pot Synthesis of Homoallyl Ketones via a Norrish Type I Reaction of Cyclopentanones

Okada, Megumi; Yamada, Keiichi; Fukuyama, Takahide; Ravelli, Davide; Fagnoni, Maurizio; Ryu, Ilhyong

doi:10.1021/acs.joc.5b01850

Cited by 31 publications

(13 citation statements)

References 49 publications

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“…In the Norrish type I (Scheme a), the photoexcited ketone decomposes reforming the C=O bond and concomitantly suffering a σC−C bond cleavage to afford an alkyl radical and a more stable acyl radical. This strategy has already found many synthetic applications and, among other radical pathways already described, the acyl radical can suffer a decarbonylative event to generate another alkyl radical.…”

Section: Photochemistry Of Carbonyl Compounds: Fundamental Aspects Anmentioning

confidence: 99%

Photochemistry of Carbonyl Compounds: Application in Metal‐Free Reactions

et al. 2019

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Synthetic organic photochemistry is an efficient and environmentally friendly alternative to assemble biologically and chemically relevant scaffolds. The photon energy allows access to reactive intermediates by using a clean energy source under mild conditions. Moreover, sustainable synthesis can be achieved by using metal-free photochemistry. In this review, the photochemistry of carbonyl compounds and their application as reagents, catalysts or promoters of metal-free photochemical transformations are discussed. Fundamental aspects and reactivity of the carbonyl compounds are briefly presented in the introduction section, followed by recent applications of carbonyl compounds in photochemical reactions. The text is organized according to the role of the carbonyl compounds in the process. First, approaches in which carbonyl compounds are employed in stoichiometric or super-stoichiometric amounts (as reaction substrates or photoinitiators) are described. Thereafter, their application as photocatalysts and photosensitizers are discussed and mechanistic studies are comprehensively presented.

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Section: Photochemistry Of Carbonyl Compounds: Fundamental Aspects Anmentioning

confidence: 99%

Photochemistry of Carbonyl Compounds: Application in Metal‐Free Reactions

et al. 2019

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“…These two reduced, hydrido-catalysts can then interact to liberate dihydrogen, closing the catalytic cycle. Combined with the knowledge that both catalysts can function in the presence of CO, 22–24 we considered whether such a strategy might be applicable to dehydroformylation.…”

Section: Introductionmentioning

confidence: 99%

Toward a mild dehydroformylation using base-metal catalysis

2017

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“…Representative approaches to access these compounds include a nucleophilic addition of an enolate or its equivalent onto π-allylpalladium complexes, [1 -4] 1,4-addition of vinyl anion equivalents to α,β-unsaturated ketones, [5 -7] Claisen rearrangements, [8 -10] etc. [11][12][13][14] Among these methods, the allylic alkylation has been most actively studied and numerous variants have been developed. [1 -4,15 -19] This strategy is based on the reaction of an allyl electrophile with an enolate equivalent.…”

Section: Introductionmentioning

confidence: 99%

“…Homoallylic ketones (γ,δ‐unsaturated ketones) have been employed as versatile building blocks in synthetic organic chemistry because they contain useful functional groups, such as carbonyl and alkenyl groups. Representative approaches to access these compounds include a nucleophilic addition of an enolate or its equivalent onto π‐allylpalladium complexes, [1–4] 1,4‐addition of vinyl anion equivalents to α,β‐unsaturated ketones, [5–7] Claisen rearrange‐ments, [8–10] etc [11–14] …”

Section: Introductionmentioning

confidence: 99%

Lewis Acid‐Mediated Decarboxylative Allylation of Enol Carbonates

Dokai

Nishizawa

Saito

et al. 2021

Helvetica Chimica Acta

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Dedicated to Prof. Peter Kündig on the occasion of his 75th birthday A homoallylic ketone can be transformed and functionalized by various synthetic reactions, and thus, is regarded as one of the representative building blocks in organic chemistry. An additional route to access homoallylic ketones, namely, a Lewis acid-mediated decarboxylative allylation of cyclic enol carbonates, prepared by fixation of carbon dioxide onto propargyl alcohols, was developed in this work. The treatment of a cyclic enol carbonate with a Lewis acid in the presence of an allylsilane resulted in the formation of a homoallylic ketone. It was found that the title reaction proceeded well by the combined use of zirconium tetrachloride with allyltrimethylsilane. The allylation occurred with high regioselectivity and the corresponding homoallylic ketones were obtained in good-to-high yields. A reaction mechanism involving the decarboxylative formation of an oxyallyl cation equivalent is proposed.

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Photocatalytic One-Pot Synthesis of Homoallyl Ketones via a Norrish Type I Reaction of Cyclopentanones

Cited by 31 publications

References 49 publications

Photochemistry of Carbonyl Compounds: Application in Metal‐Free Reactions

Photochemistry of Carbonyl Compounds: Application in Metal‐Free Reactions

Toward a mild dehydroformylation using base-metal catalysis

Lewis Acid‐Mediated Decarboxylative Allylation of Enol Carbonates

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