Radicals masquerading as electrophiles: Dual orbital effects in nitrogen-philic acyl radical cyclization and related addition reactions

Carl H. Schiesser, Uta Wille, Hiroshi Matsubara, Ilhyong Ryu

    Research output: Contribution to journalArticlepeer-review

    115 Scopus citations

    Abstract

    Free-radical chemistry has come a long way in a relatively short period of time. The synthetic practitioner takes for granted the wealth of mechanistic and rate constant data now available and can apply free-radical techniques to the synthesis of many different classes of target molecule with confidence. Despite this, there are still mechanistic anomalies that need to be addressed. This Account highlights recent work involving nucleophilic radicals with low-lying unoccupied orbitais, such as acyl, oxyacyl, silyl, stannyl, and germyl radicals. Through interesting singly occupied molecular orbital (SOMO)-π* and highest occupied molecular orbital (HO-MO)-lowest unoccupied molecular orbital (LUMO) interactions during these reactions, the radicals involved are able to mask as electrophiles, providing high levels of regiocontrol and efficient methods for the synthesis of important heterocycles.

    Original languageEnglish
    Pages (from-to)303-313
    Number of pages11
    JournalAccounts of Chemical Research
    Volume40
    Issue number5
    DOIs
    StatePublished - 1 May 2007

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