Application of correlation interaction coefficients. Part 1. Structure–reactivity relationship of phenylethyl arenesulfonates under high pressure

Abstract

The rates for the reaction of (Z)-phenylethyl (X)-benzenesulfonates with (Y)-pyridines under pressure in acetonitrile at 60°C were measured by an electrical conductivity method. From the values of r X , r Y and r Z , it was concluded that bond formation between the nucleophile and reaction center is more advanced in the transition state (TS). The magnitude of the correlation interaction term, r ij , was used to determine the structure of the transition state for the S N reaction. As the pressure increases, the Hammett reaction constants r X and r Y decrease, but the correlation interaction coefficients, r XZ and r YZ , increase. The results indicate that the reaction of (Z)-phenylethyl (X)-benzenesulfonates with (Y)-pyridines probably proceeds via a dissociative S N 2 reaction and with increasing pressure the TS moves to an early position. This result agrees with the MOFJ diagram interpretation and shows that the correlation interaction term, r ij , can be a useful tool for determining the structure of the TS.

Sulfonyl transfer mechanism in C–S coupling of phenylmagnesium bromide with phenyl arenesulfonates

“…Reactions of nucleophiles with aryl arenesulfonates at S atom are known to take place generally by stepwise S N a mechanism or concerted S N 2(S) mechanism (Scheme 3) [28][29][30][31][32][33]. S N a mechanism involves a pentacoordinate intermediate [29,33] and S N 2(S) mechanism proceeds via a transition state in which bond formation and bond breaking occur synchronously.…”

“…There are various mechanistic possibilities for S-O bond cleavage in aryl arenesulfonates and there has been considerable interest in the kinetics and mechanism of the sulfonyl transfer reactions of oxygen, sulfur and nitrogen anionic nucleophiles [28][29][30][31][32][33]. However, no work has been published on the mechanism of the reactions of organolithiums and Grignard reagents with sulfonates at sulfur center.…”

An insight into the C–S coupling mechanism of aryl Grignard reagents with aryl arenesulfonates

“…The kinetics and mechanism of C-C coupling of sulfonates [10-13, 15, 17, 18, 24] and also C-heteroatom coupling of sulfonates with heteroatom nucleophiles [25][26][27][28][29][30][31][32][33] have been thoroughly investigated. However, the kinetic and mechanistic details of C-S coupling of aryl Grignard reagents with aryl arenesulfonates have been recently reported by Erdik et al [34][35][36].…”