The<i>gem-</i>Dialkyl Effect in Electron Transfer Reactions:  Rapid Synthesis of Seven-Membered Rings through an Electrochemical Annulation

Sperry, Jeffrey B.; Wright, Dennis L.

doi:10.1021/ja051826+

Cited by 41 publications

(18 citation statements)

References 16 publications

(13 reference statements)

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“…The electrochemical furan annulations were developed into a general method of synthesis. 41 Moeller applied this methodology to a creative synthesis of alliacol ( 71 ) in 2004. 42 Other notable examples of electrochemical transformations can be found in the cited reviews.…”

Section: Discussionmentioning

confidence: 99%

Benefits of Unconventional Methods in the Total Synthesis of Natural Products

Hudlický

2018

ACS Omega

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This article provides a survey of four “unconventional” methods employed in the synthesis of natural products in the Hudlicky group. The utility of flash vacuum pyrolysis is highlighted by examples of many natural products attained via vinylcyclopropane–cyclopentene rearrangement and its heterocyclic variants. Preparative organic electrochemistry was used in oxidations and reductions with levels of selectivity unattainable by conventional methods. Yeast reduction of ketoesters was featured in the total synthesis of pyrrolizidine alkaloids. Finally, the use of toluene dioxygenase-mediated dihydroxylations in enantioselective synthesis of natural products concludes this presentation. Recently, synthesized targets in the period 2010–2019 are listed in the accompanying table. The results of research from the Hudlicky group are placed in appropriate context with the work of others, and a detailed guide to the current literature is provided.

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Section: Discussionmentioning

confidence: 99%

Benefits of Unconventional Methods in the Total Synthesis of Natural Products

Hudlický

2018

ACS Omega

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“…[801][802][803][804][805][806][807] These electrochemical annulations are presumed to involve initial oxidation of the silyl enol ether moiety rather than the furyl group. 800 Additional heterocycles that have been utilized consist of imidazoles, 81 pyrroles 794 as well as thiophenes. [808][809][810] The applicability of the anodic olefin coupling reaction between silyl enol ethers and furans has also been exploited in syntheses of natural products.…”

Section: Electrochemical Oxidative Cross-couplingsmentioning

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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“…The second step involves anodic coupling of the furan and the silyl enol ether to form the cis-fused six-membered ring 97 with high stereoselectivity (Scheme 6.38) [88]. The reaction can be extended to the formation of seven-membered ring fused furan 98 [89]. However, the substituent on the 3-position of cyclopentanone is important for the formation of a seven-membered ring fused furans.…”

Section: Disubstituted Furansmentioning

confidence: 99%

“…Scheme 6.84 shows a recent example of the construction of the complex tetracyclic core 186 of guanacastepenes, obtained as a single diastereoisomer, by such an electron transfer reaction [157]. A gem-dialkyl effect has been identified as essential for the efficient formation of a seven-membered ring in this type of reaction [89,158].…”

Section: Reactions With Oxidizing Reagentsmentioning

confidence: 99%