Details

Autor(en) / Beteiligte

• Lee, Byung Joo
• DeGlopper, Kimberly S.
• Yoon, Tehshik P.

Titel

Site‐Selective Alkoxylation of Benzylic C−H Bonds by Photoredox Catalysis

Ist Teil von

• Angewandte Chemie (International ed.), 2020-01, Vol.59 (1), p.197-202

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2020

Link zum Volltext

Quelle

MEDLINE

Beschreibungen/Notizen

• Methods that enable the direct C−H alkoxylation of complex organic molecules are significantly underdeveloped, particularly in comparison to analogous strategies for C−N and C−C bond formation. In particular, almost all methods for the incorporation of alcohols by C−H oxidation require the use of the alcohol component as a solvent or co‐solvent. This condition limits the practical scope of these reactions to simple, inexpensive alcohols. Reported here is a photocatalytic protocol for the functionalization of benzylic C−H bonds with a wide range of oxygen nucleophiles. This strategy merges the photoredox activation of arenes with copper(II)‐mediated oxidation of the resulting benzylic radicals, which enables the introduction of benzylic C−O bonds with high site selectivity, chemoselectivity, and functional‐group tolerance using only two equivalents of the alcohol coupling partner. This method enables the late‐stage introduction of complex alkoxy groups into bioactive molecules, providing a practical new tool with potential applications in synthesis and medicinal chemistry. Partner up: Photocatalysis offers a one‐step strategy to selectively functionalize the benzylic positions of electron‐rich arenes with alcohols. It merges the photoredox activation of arenes with copper(II)‐mediated oxidation of the resulting benzylic radicals, enabling the introduction of benzylic C−O bonds with high site selectivity, chemoselectivity, and functional‐group tolerance using only two equiv of the alcohol coupling partner.