Ortho-selective C–H arylation of phenols with N-carboxyindoles under Brønsted acid- or Cu(i)-catalysis. Issue 4 (13th January 2022)

• Record Type: Journal Article
• Authors: Nguyen, Nguyen H.; Oh, Soo Min; Park, Cheol-Min; Shin, Seunghoon
• Is Part Of: Chemical science. Volume 13:Issue 4(2022)
• Page Start: 1169
• Page End: 1176
• Publication Date: 2022-01-13
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d1sc06157g
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Control over chemo- and regioselectivity is a critical issue in the heterobiaryl synthesis via C–H oxidative coupling. To address this challenge, a strategy to invert the normal polarity of indoles was developed. Abstract : Control over chemo- and regioselectivity is a critical issue in the heterobiaryl synthesis via C–H oxidative coupling. To address this challenge, a strategy to invert the normal polarity of indoles in the heterobiaryl coupling was developed. With N -carboxyindoles as umpoled indoles, an exclusively ortho -selective coupling with phenols has been realized, employing a Brønsted acid- or Cu(i )-catalyst (as low as 0.01 mol%). A range of phenols and N -carboxyindoles coupled with exceptional efficiency and selectivity at ambient temperature and the substrates bearing redox-active aryl halides (–Br and –I) smoothly coupled in an orthogonal manner. Notably, preliminary examples of atropselective heterobiaryl coupling have been demonstrated, based on a chiral disulfonimide or a Cu(i )/chiral bisphosphine catalytic system. The reaction was proposed to occur through SN 2′ substitution or a Cu(i )–Cu(iii ) cycle, with Brønsted acid or Cu(i ) catalysts, respectively.