Electrochemical Radical Selenylation/1,2-Carbon Migration and Dowd–Beckwith-Type Ring-Expansion Sequences of Alkenylcyclobutanols

Abstract

Electrochemical oxidative radical selenylation/1,2-carbon migration and Dowd–Beckwith-type ring-expansion sequences of alkenylcyclobutanols were developed in this study. This approach is environmentally benign and uses shelf-stable diselenides as selenium radical precursors and electrons as oxidizing reagents. The present protocol offers a facile way to prepare β-selenated cyclic ketone derivatives. Under Dowd–Beckwith-type rearrangement, it can afford the corresponding one-carbon ring-expanded ketones.

Synthesis of Seleno Oxindoles via Electrochemical Cyclization of N‐arylacrylamides with Diorganyl Diselenides

“…On the basis of the abovementioned results and reported literature, [26] a possible mechanism for the electrochemical cyclization is presented in Scheme 6. The reaction could be initiated by the formation of seleno radical A and selenium cation B via anodic oxidation.…”

Copper‐promoted Synthesis of β‐Selenylated Cyclopentanones via Selenylation and 1,2‐Alkyl Migration Sequences of Alkenyl Cyclobutanols

“…Organic selenium compounds have attracted much attention in medicinal and synthetic chemistry because of their use as therapeutic agents and synthetic intermediates in organic synthesis . Recently, our laboratory reported oxidative selenylation/1,2‐alkyl migration cascades via the semipinacol‐type rearrangement of alkenyl cyclobutanols under electrochemical or photocatalytic reaction conditions (Scheme (a)) . Despite the above achievements, a more efficient protocol is still needed.…”

Insights into the Recent Synthetic Advances of Organoselenium Compounds

“…In this direction, Yubin Kim et al, explored alkenyl cyclobutanols for the synthesis of β-selenated ketones under copper mediated [105] and electrochemical reaction conditions. [106,107] The reaction was optimized with 1-(1-phenylvinyl)cyclobutanol 45 and diphenyl diselenide as the model substrates, catalyzed by copper iodide in DMSO under an open air condition (Scheme 20). The coppermediated reaction commences with the formation of electrophilic selenium species RSe + , which reacts with alkenyl cyclobutanol 45 to form seleniranium ion, then undergoes semipinacol-type rearrangement/migration leading to the βselenated cyclopentanone 46.…”