Anodic oxidation of carbamates using organothio groups as electroauxiliaries

Sugawara, Masanobu; Mori, Keisuke; Yoshida, Jun‐ichi

doi:10.1016/s0013-4686(97)85473-4

Cited by 40 publications

(16 citation statements)

References 31 publications

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“…Subjecting 7 to an excess charge of 10.0 F/mol resulted in traces of what was tentatively assigned a double dehydrogenative coupled product, but no evidence of ring opening to an aldehyde-oxidation level product was observed. 57 Differentially N,N′-substituted tertiary amide bond containing systems are reported to afford a 3:1 selectivity 58 for electrochemical dehydrogenative coupling of a methyl C−H bond over the benzyl C−H bond. To our surprise, in entry 4, complete regioselectivity for methyl C−N scission over the benzylic methylene bond was observed.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Electrically Driven N(_sp²)–C(_sp^2/3) Bond Cleavage of Sulfonamides

Wetzel

Jones

2020

ACS Sustainable Chem. Eng.

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Sulfonamides are a privileged class of functional groups in medicinal chemistry and an important class of protecting groups in organic synthesis. We report the discovery and development of unexpected electrically driven N(sp 2 )−C(sp 2 ) and N(sp 2 )−C(sp 3 ) bond cleavage reactions alongside a dehydrogenative C−O bond coupling reaction under batch and electroflow conditions. Intra-molecular trapping experiments with the diuretic hydrochlorothiazide gave insight into the intermediacy of an N-sulfonyliminium ion en route to the related drug metabolite, chlorothiazide. Using only electrons as the oxidant, this is a green and sustainable technological advancement for sulfonamide deprotection chemistry and drug metabolism studies.

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Section: ■ Results and Discussionmentioning

confidence: 99%

“…Differentially N , N′ -substituted tertiary amide bond containing systems are reported to afford a 3:1 selectivity for electrochemical dehydrogenative coupling of a methyl C–H bond over the benzyl C–H bond. To our surprise, in entry 4, complete regioselectivity for methyl C–N scission over the benzylic methylene bond was observed.…”

Section: Resultsmentioning

confidence: 99%

Electrically Driven N(_sp²)–C(_sp^2/3) Bond Cleavage of Sulfonamides

Wetzel

Jones

2020

ACS Sustainable Chem. Eng.

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“…50 This concept relies on the inherent properties of the electroauxiliaries to lower the oxidation potential of the substrate, thereby facilitating and providing enhanced control of the anodic oxidation of the substrate. The electroauxiliaries employed in Shono-type oxidations have typically been silylbased, [199][200][201][202][203][204][205][206][207][208][209][210][211][212][213] although 2,4,6-trimethoxyphenyl 214 and sulfurbased [215][216][217] electroauxiliaries have also been employed.…”

Section: Shono-type Anodic Oxidationsmentioning

confidence: 99%

Electrochemical strategies for C–H functionalization and C–N bond formation

2018

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Conventional methods for carrying out carbon-hydrogen functionalization and carbon-nitrogen bond formation are typically conducted at elevated temperatures, and rely on expensive catalysts as well as the use of stoichiometric, and perhaps toxic, oxidants. In this regard, electrochemical synthesis has recently been recognized as a sustainable and scalable strategy for the construction of challenging carbon-carbon and carbon-heteroatom bonds. Here, electrosynthesis has proven to be an environmentally benign, highly effective and versatile platform for achieving a wide range of nonclassical bond disconnections via generation of radical intermediates under mild reaction conditions. This review provides an overview on the use of anodic electrochemical methods for expediting the development of carbon-hydrogen functionalization and carbon-nitrogen bond formation strategies. Emphasis is placed on methodology development and mechanistic insight and aims to provide inspiration for future synthetic applications in the field of electrosynthesis.

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“…Then, under non-oxidative conditions, a nucleophile is introduced which would otherwise be destroyed during the electrolysis. 57 Considering the oxidation of unsymmetrical substrate molecules, regioselective electrochemical transformations can be achieved by prior introduction of an electroauxiliary, a functional group (i.e., silyl [58][59][60] or arylthio groups 61,62 ) that promotes electron transfer by adjusting the oxidation potential and directing the formation of the C=N bond through their own elimination. The 'cation pool' method therefore provides a useful one-pot procedure under mild conditions and has been extensively studied.…”

Section: Shono-type Oxidationmentioning

confidence: 99%

Anodic Oxidation as an Enabling Tool for the Synthesis of Natural Products

Geske

Sato²,

Opatz³

2020

Synthesis

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Electrochemistry provides a valuable toolbox for organic synthesis and offers an appealing, environmentally benign alternative to the use of stoichiometric quantities of chemical oxidants or reductants. Its potential to control current efficiency along with providing alternative reaction conditions in a classical sense makes electrochemistry a suitable method for large-scale industrial transformations as well as for laboratory applications in the synthesis of complex molecular architectures. Even though research in this field has intensified over the recent decades, many synthetic chemists still hesitate to add electroorganic reactions to their standard repertoire, and hence, the full potential of preparative organic electrochemistry has not yet been unleashed. This short review highlights the versatility of anodic transformations by summarizing their application in natural product synthesis.1 Introduction2 Shono-Type Oxidation3 C–N/N–N Bond Formation4 Aryl–Alkene/Aryl–Aryl Coupling5 Cycloadditions Triggered by Oxidation of Electron-Rich Arenes6 Spirocycles7 Miscellaneous Transformations8 Future Prospects

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Anodic oxidation of carbamates using organothio groups as electroauxiliaries

Cited by 40 publications

References 31 publications

Electrically Driven N(_sp²)–C(_sp^2/3) Bond Cleavage of Sulfonamides

Electrically Driven N(_sp²)–C(_sp^2/3) Bond Cleavage of Sulfonamides

Electrochemical strategies for C–H functionalization and C–N bond formation

Anodic Oxidation as an Enabling Tool for the Synthesis of Natural Products

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Anodic oxidation of carbamates using organothio groups as electroauxiliaries

Cited by 40 publications

References 31 publications

Electrically Driven N(sp2)–C(sp2/3) Bond Cleavage of Sulfonamides

Electrically Driven N(sp2)–C(sp2/3) Bond Cleavage of Sulfonamides

Electrochemical strategies for C–H functionalization and C–N bond formation

Anodic Oxidation as an Enabling Tool for the Synthesis of Natural Products

Contact Info

Product

Resources

About

Electrically Driven N(_sp²)–C(_sp^2/3) Bond Cleavage of Sulfonamides

Electrically Driven N(_sp²)–C(_sp^2/3) Bond Cleavage of Sulfonamides