Asymmetric Diastereoselective Synthesis of Spirocyclopropane Derivatives of Oxindole

Abstract

A new asymmetric organocatalytic synthesis of spirocyclopropane oxindoles has been developed. The method is based on the Michael addition of N‐Boc‐protected 3‐chlorooxindole to unsaturated 1,4‐dicarbonyl compounds, affording trans‐substituted spirocyclopropane oxindole derivatives in high diastereo‐ and enantioselectivity.

Molecular diversity of spirooxindoles. Synthesis and biological activity

“…Further, spirocyclopropanes have also been reported from diazo compounds and alkenes in the presence of expensive transition metals, such as Rh 2 (OAc) 4 , CuOTf, Hg(OTf) 2 or Au(I)-complexes [220,221]. The disadvantage of the metal-catalyzed process is that heteroatom containing alkenes could bind tightly to a transition metal present in the catalyst, resulting in loss of their catalytic activity.…”

Syntheses and Applications of Spirocyclopropyl Oxindoles: A Decade Review

“…However, in all reactions, a little amount of uncyclized Michael adduct 88 was formed, which could not be avoided. [ 45 ] Further, same group presented the reaction of 10 with α,β‐unsaturated aldehydes 89 and 3‐alkenyl oxindoles to furnish the highly substituted spirocyclopropanes. [ 46 ] Application of proline‐derived amino‐catalyst X was feasible for the conversion of 3‐chlorooxindoles and α,β‐unsaturated aldehydes into 90 .…”

High-Selective One-Pot Synthesis of Spirocyclopropane Pyrazolones Promoted by 4-Dimethylaminopyridine

“…[17] Asymmetric organocatalytic reaction of unsaturated 1,4-diketones and 3-chlorooxindoles generated a series of spiro-oxindoles with higher enantioselectivities (Scheme 1a). [18] Triphenylarsine has been used as a catalyst for the synthesis of cyclopropane-indan-diones using the cyclopropanation of alkene with phenacyl bromide (Scheme 1b). [19] Furthermore, the reaction of 4-arylidene-3-methyl-1-phenyl-pyrazolin-5-one with arsonium salt was resulted in spiro-cyclopropane-pyrazoles in the presence of KF• 2H 2 O (Scheme 1c).…”