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Selektivität bei der Umsetzung von Carbokationen mit Nucleophilen, 2. Solvolyse‐Mechanismen bei 7‐Norbornyl‐trifluormethansulfonaten
Author(s) -
Martínez Antonio García,
Barcina José Osío,
Hernando Manuel Montero
Publication year - 1985
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19851180632
Subject(s) - chemistry , 2 norbornyl cation , carbocation , nucleophile , solvolysis , selectivity , medicinal chemistry , norbornane , stereochemistry , organic chemistry , catalysis , hydrolysis
Selectivity in the Reaction of Carbocations with Nucleophiles, 2. Solvolytic Mechanisms of 7‐Norbornyl Trifluoromethanesulfonates The reactions of 7,7‐bis(trifluoromethylsulfonyloxy)norbornane ( 4 ) with several metal cyanides in dipolar aprotic solvents are studied. The results obtained (Table 1) lead to the conclusion that the solvolysis of 7‐substituted 7‐norbornyl trifluoromethanesulfonates takes place either according to a k c mechanism or with fission of the S O bond. In no instance is a C O fission following an S N 2 mechanism to be expected. – The selectivity of the reaction of the intermediate carbocations with nucleophiles cannot be explained by means of N + correlations nor by the reactivity‐selectivity relationship, but can be rationalized according to the HSAB principle.