Stereoselective Construction of Vicinal Quaternary Stereocenters via the 1,6-Conjugate Addition of β,β-Disubstituted N-Sulfinyl Metalloenamines to Isatin-Derived para-Quinone Methides

Abstract

A 1,6-conjugate addition reaction of β,β-disubstituted N-tert-butanesulfinyl metalloenamines, generated via stereospecific α-deprotonation of enantioenriched α,α-disubstituted ketimines or deprotonation of the NH in geometry-defined enesulfinamides, with isatin-derived para-quinone methides is developed to build vicinal quaternary stereocenters with high stereocontrol. The resulting 3,3-disubstituted oxindoles contain a less-accessible acyclic quaternary stereogenic carbon substituted with two sterically and electronically similar groups at the α-position of the imino group. This protocol constitutes a rare example of the stereoselective construction of vicinal quaternary stereocenters via the conjugate addition of acyclic enolates/aza-enolates bearing two similar β-substituents.

Key words

N-sulfinyl metalloenamines - conjugate addition - deprotonation - quaternary stereocenter - stereoselectivity

Publication History

Received: 13 November 2023

Accepted after revision: 06 December 2023

Accepted Manuscript online:
06 December 2023

Article published online:
16 January 2024

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