Visible‐Light‐Initiated Manganese Catalysis for C−H Alkylation of Heteroarenes: Applications and Mechanistic Studies. (26th October 2017)

• Record Type: Journal Article
• Authors: Nuhant, Philippe; Oderinde, Martins S.; Genovino, Julien; Juneau, Antoine; Gagné, Yohann; Allais, Christophe; Chinigo, Gary M.; Choi, Chulho; Sach, Neal W.; Bernier, Louise; Fobian, Yvette M.; Bundesmann, Mark W.; Khunte, Bhagyashree; Frenette, Mathieu; Fadeyi, Olugbeminiyi O.
• Is Part Of: Angewandte Chemie. Volume 129:Number 48(2017)
• Page Start: 15511
• Page End: 15515
• Publication Date: 2017-10-26
• Subjects: C-H-Alkylierungen -- Dichtefunktionalrechnungen -- Mangan -- Minisci-Reaktion -- Redoxchemie; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201707958
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: A visible‐light‐driven Minisci protocol that employs an inexpensive earth‐abundant metal catalyst, decacarbonyldimanganese Mn2 (CO)10, to generate alkyl radicals from alkyl iodides has been developed. This Minisci protocol is compatible with a wide array of sensitive functional groups, including oxetanes, sugar moieties, azetidines, tert ‐butyl carbamates (Boc‐group), cyclobutanes, and spirocycles. The robustness of this protocol is demonstrated on the late‐stage functionalization of complex nitrogen‐containing drugs. Photophysical and DFT studies indicate a light‐initiated chain reaction mechanism propagated by . Mn(CO)5 . The rate‐limiting step is the iodine abstraction from an alkyl iodide by . Mn(CO)5 .