Divergent synthesis of indoles, oxindoles, isocoumarins and isoquinolinones by general Pd-catalyzed retro-aldol/α-arylation. Issue 44 (21st October 2016)

• Record Type: Journal Article
• Authors: Zhang, Song-Lin; Yu, Ze-Long
• Is Part Of: Organic & biomolecular chemistry. Volume 14:Issue 44(2016)
• Page Start: 10511
• Page End: 10515
• Publication Date: 2016-10-21
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c6ob01979j
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : Divergent synthesis of indoles, oxindoles, isocoumarins and isoquinolinones is achieved by a general Pd-catalyzed retro-aldol reaction of β-hydroxy ketones/esters with aryl halides bearing an ortho -nitro, -ester or -nitrile group. DFT insights have been presented to rationalize the experimental observations and the chemoselectivity. Abstract : Divergent synthesis of indoles, oxindoles, isocoumarins and isoquinolinones is described in this report by using a general Pd-catalyzed tandem reaction of β-hydroxy carbonyl compounds with aryl halides bearing an ortho -nitro, -ester or -cyano substituent. A key retro-aldol/α-arylation reaction is involved that merges classic Pd cross-coupling chemistry with novel Pd-promoted retro-aldol C–C activation to produce α-arylated ketones or esters. Subsequent intramolecular condensation of the carbonyl with the ortho -synthon gives target heterocycles. The use of common, commercially available and cheap substrates and catalyst system adds additional synthetic advantages to the conceptual significance.