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Polar-Radical Cyclization Cascades with Magnesiated Nitriles
Journal article   Peer reviewed

Polar-Radical Cyclization Cascades with Magnesiated Nitriles

Stephen Bolgunas, Ehecatl Paleo, Embarek Alwedi, Yunjing Wei, Taylor M. Keller and Fraser F. Fleming
Organic letters, v 25(19), pp 3512-3516
19 May 2023
PMID: 37142576

Abstract

Naphthalene converts magnesiated ω-alkenylnitriles into bi- and tricyclic ketones via a polar-radical addition–cyclization cascade. One-electron oxidation of magnesiated nitriles generates nitrile-stabilized radicals that cyclize onto a pendant olefin and then rebound onto the nitrile through a reduction–cyclization sequence; subsequent hydrolysis affords a diverse array of bicyclo[3.2.0]­heptan-6-ones. Combining the polar-radical cascade with a 1,2:1,4-carbonyl-conjugate addition generates complex cyclobutanones containing four new carbon–carbon bonds and four chiral centers in one synthetic operation.

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Industry collaboration
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International collaboration
Web of Science research areas
Chemistry, Organic
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