Chitosan catalyzed synthesis and mechanistic study of steroidal 2H-pyran ring formation

Abstract

A simple and convenient method is reported for the preparation of steroidal 2H-pyran 2 by reacting 3β-acetoxy cholest-5-ene-7-one 1 with N-benzyl-2-cyanoacetamide in presence of chitosan, a green and heterogeneous catalyst. The product 2 was characterized by using NMR (1H and 3C), IR, and mass spectroscopy. The mechanism of 2H-pyran ring formation is described by employing theoretical B3LYP/6-31G (d) density functional method. The reaction undergoes via formation of two intermediates A and B, and each intermediate undergoes through a transition state TS1 and TS2. The molecular properties like relative energy and FMO analysis were used to explain the mechanism of the reaction. The HOMOs and LUMOs were found in support of the present reaction mechanism. The stability of all the calculated structures which includes reactant (1a), intermediates (A and B), product (2a) as well as TS1 and TS2 transition states, was supported by calculating their energy minima and fundamental frequencies.