Diastereoselective Palladium Catalyzed Carbenylative Amination of ortho‐Vinylanilines with 3‐Diazoindolin‐2‐ones

Abstract

A diastereoselective palladium catalyzed carbenylative amination of ortho‐vinylaniline with 3‐diazoindolines‐2‐one have been accomplished for the synthesis of various tetrasubstituted indoline fused spirooxindole with good yields and diastereoselectivity. Notable features of the method include construction of two contiguous tetrasubstituted carbon stereocenters via C−N and C−C bond formation in single operation, wide functional group tolerance and high atom and step economy. Importantly, the present reaction was also extended to one‐pot conversion of tosylhydrazones and ortho‐vinylanilines to spirooxindole derivatives.

Stereoselective synthesis and applications of spirocyclic oxindoles

“…250 Very recently, Anbarasan reported Pd-catalysed amination of 3-diazooxindoles with ortho-vinyl anilines. 251 Photoredox. Zhao and Jiang have reported a photoredox asymmetric phosphoric acid catalysed combination of α-amino radicals and 3-aryloxindole radicals (Scheme 54).…”

Catalytic Functionalization of Metallocarbenes Derived from α‐Diazocarbonyl Compounds and Their Precursors

“…Similar reactivity was observed with isatin-based diazo compounds 43 and ortho-vinylaniline derivatives 37. [19] Electronically and sterically different spiro-oxindole derivatives 44 were synthesized in good yield via a carbenylative amination approach in the presence of palladium-catalyst (Scheme 8). Interestingly, spiro-oxindoles were also synthesized quite easily from corresponding N-tosylhydrazones in one-pot reaction, instead of generating diazo compound 43.…”

Photoinduced [3+2] Annulation of Alkene with o-Iodoanilines: An Expedient Approach to Indolines

“…Subsequently, the alkene scope was extended to alkenes with a cycloalkane fused-benzene scaffold. Gladly, their cross-coupling with 2-iodo-N-methylaniline constitutes an expedient access to spiroindolines, the structure of which is frequently occurring in pharmaceuticals and natural products, 42 whereas relevant preparation methods for this interesting motif are extremely rare. Given this, several types of structurally diverse spiroindolines were prepared via this protocol.…”