Synthesis of Benzylic Alcohols by C–H Oxidation

Tanwar, Lalita; Börgel, Jonas; Ritter, Tobias

doi:10.1021/jacs.9b09496

Cited by 99 publications

(91 citation statements)

References 49 publications

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“…[1][2][3][4][5] Specifically, selective functionalization of the ubiquitous benzylic C-H bond in organic molecules has a broad impact, ranging from upgrading feedstock alkylarenes for functional molecule synthesis to late-stage modifications of complex pharmaceuticals and bioactive structures (Scheme 1a). [6][7][8][9][10][11][12][13][14][15][16][17][18] For instance, approximately 30% of the top-selling drugs contain at least one (hetero)benzylic C-H bond, and the selective functionalization of these C-H bonds could potentially change their metabolic stabilities and regulate bioactivities. Information gathered by the Njardarson group with data from DrugTopics & Pharmacompass.…”

Section: Introductionmentioning

confidence: 99%

Copper-Catalyzed Benzylic C–H Bond Thiocyanation: Enabling Late-Stage Diversifications

2021

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The rapid growth of using C-H bond as cross-coupling partners is reshaping the landscape of organic synthesis. C(sp 3 )-H functionalization via hydrogen atom transfer (HAT) represents the most compelling strategy in this avenue. Here, we demonstrate an efficient method for benzylic C-H bond thiocyanation via copper-catalyzed radical relay. The reaction exhibits broad substrate scope and exquisite benzylic selectivity with C-H substrates as limiting reagents. In addition, the benzyl thiocyanates are readily converted to other pharmaceutically important motifs, including isothiocyanate, thiourea, and others, highlighting the broad utility of this method.

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Section: Introductionmentioning

confidence: 99%

Copper-Catalyzed Benzylic C–H Bond Thiocyanation: Enabling Late-Stage Diversifications

2021

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“…This is consistent with the mechanistic observations, suggesting the presence of the radical cation intermediates 14-1 or 16-1. [24] Based on the experimental results and literature, [25] we propose the reaction mechanism depicted in Figure 5 c. First, PC is activated to generate excited PC* by visible light irradiation.…”

Section: Entrymentioning

confidence: 87%

Direct Access to Primary Amines from Alkenes by Selective Metal‐Free Hydroamination

Chen

Shu

2021

Angewandte Chemie

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Direct and selective synthesis of primary amines from easily available precursors is attractive yet challenging. Herein, we report the rapid synthesis of primary amines from alkenes via metal-free regioselective hydroamination at room temperature. Ammonium carbonate was used as ammonia surrogate for the first time, allowing for efficient conversion of terminal and internal alkenes into linear, a-branched, and atertiary primary amines under mild conditions. This method provides a straightforward and powerful approach to a wide spectrum of advanced, highly functionalized primary amines which are of particular interest in pharmaceutical chemistry and other areas.

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“…Notably, in 2019, Ritter's group [62] reported a method for the synthesis of benzylic alcohols by selective monooxidation of alkylated benzenes, in which bis(methanesulfonyl) peroxide severs as an oxidant (Scheme 12). Their method achieved the conversion of benzylic C-H bond to benzylic alcohols, and they proposed that the reaction proceeds via a PCET pathway.…”

Section: Scheme 3 Homo-dimerization Of 3-aryl Oxindoles Via Pcet Pathwaysmentioning

confidence: 99%

Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Zhou¹,

Kong²,

Liu³

2021

Chinese Journal of Organic Chemistry

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Proton-coupled electron transfer (PCET) reactions are a kind of unconventional redox reactions, which exhibit special reactivities and selectivities due to their unique interdependent electron-proton transfer mechanisms. There are three possible pathways of PCET processes, including stepwise electron transfer followed by proton transfer (ETPT), proton transfer followed by electron transfer (PTET), and concerted pathway in which electron and proton transfer synchronously (CEPT), avoiding intermediates with high energy. These reactions have been playing a key role in numerous areas in organic chemistry, inorganic chemistry, bioorganic chemistry, organometallic and material chemistry, including the redox processes in natural and artificial systems, such as the activation for small molecules. Recently, the application of PCET reactions in organic synthesis has received a great deal of attentions and interests. Being accompanied by the development of electrochemical methods and photocatalysts, more and more novel reactions in electrochemistry and photochemistry involve PCET processes have been reported. Applying these electrochemical and photochemical methods, the activation of X-H bond has been achieved via PCET processes, including C-H bond, N-H bond, P-H bond, S-H bond or O-H bond. Thus, based on these crucial processes, a number of vital structures and fundamental frameworks can be synthesized, and various synthetic building blocks and natural products have been attained. For example, pharmaceutical building blocks like 2°-piperidines can be cyanated at their α-position; substituted dimeric pyrroloindolines such as (-)-calycanthidine, (-)-chimonanthine, and (-)-psychotriasine have also been successfully synthesized via PCET mechanism. Moreover, not only the products of reduction of multiple bonds (C＝ Y bond such as C＝C bond, C＝N bond and C＝O bond), but also the products of self/cross-coupling have been achieved via PCET mechanism. In this review, the recent applications and developments of PCET mechanism in organic synthesis are summarized, including new catalyst systems and new reagents, especially with electrochemical and photochemical methodologies. The future of this area has also been demonstrated from both experimental and theoretical aspects. Keywords proton-coupled electron transfer; organic synthesis; radical reactions; functionalization

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Synthesis of Benzylic Alcohols by C–H Oxidation

Cited by 99 publications

References 49 publications

Copper-Catalyzed Benzylic C–H Bond Thiocyanation: Enabling Late-Stage Diversifications

Copper-Catalyzed Benzylic C–H Bond Thiocyanation: Enabling Late-Stage Diversifications

Direct Access to Primary Amines from Alkenes by Selective Metal‐Free Hydroamination

Applications of Proton-Coupled Electron Transfer in Organic Synthesis

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