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Polar versus steric effects in the solvolysis of 6 endo ‐substituted 2 endo ‐norbornyl p ‐toluenesulfonates. Norbornanes , Part 8
Author(s) -
Grob Cyril A.,
Günther Bettina,
Hanreich Reinhard
Publication year - 1982
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.19820650718
Subject(s) - 2 norbornyl cation , chemistry , solvolysis , steric effects , substituent , medicinal chemistry , polar , reaction rate constant , stereochemistry , organic chemistry , kinetics , hydrolysis , physics , quantum mechanics , astronomy
The solvolysis rates and products of the 6 endo ‐R‐substituted 2 endo ‐norbornyl toluenesulfonates 6a – 6i have been determined. The rates of 6a – 6g correlate with the inductive constants σ I qthe 6 endo ‐substituents and are not related to the size of the latter. It is therefore concluded that polar rather than steric effects control the exo / endo ‐rate ratios of norbornyl sulfonates. Products are derived mainly from rearranged 6 exo ‐R‐norbornyl cations when the substituent is an electron donor and from unrearranged 6 endo ‐R‐substituted cations when the substituent is an electron acceptor.