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Carbon Participation in the Solvolysis of 6‐ and 7‐Substituted 2‐Norbornyl p ‐Toluenesulfonates. Norbornanes, Part 11
Author(s) -
Flury Peter,
Grob Cyril A.
Publication year - 1983
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19830660709
Subject(s) - 2 norbornyl cation , chemistry , solvolysis , substituent , cationic polymerization , carbon atom , stereochemistry , medicinal chemistry , organic chemistry , ring (chemistry) , hydrolysis
Abstract The solvolysis rates and products of several 7‐ anti ‐substituted 2‐ endo ‐norbornyl p ‐toluenesulfonates 11 have been determined and compared with those of the previously reported 6‐ exo ‐substituted 2‐ exo ‐norbornyl p ‐toluenesulfonates 1. Although the number of bonds between the substituent and the reaction site is the same in the two series, the inductive effect of the substitutents is transmitted far more strongly in the 6‐ exo ‐2‐ exo ‐series 1 than in the 7‐ anti ‐2‐ endo ‐series 11 ; i.e. their inductivities differ widely. It is concluded that through space induction involves graded bridging of the substituent‐bearing C‐atom to the incipient cationic center at C(2) and that this involves differential bridging strain. The different reactivities of unsubstituted 2‐ exo ‐ and 2‐ endo ‐norbornyl derivatives can then be ascribed to a stereoelectronic effect.