Solvolysis of (Z)-5-Trimethylstannyl 2-Adamantyl p-Bromobenzenesulfonate: Mechanistic Implications of a Record-Breaking Secondary α-Deuterium Kinetic Isotope Effect for an SN1 Substrate
- 22 May 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 68 (13) , 5399-5402
- https://doi.org/10.1021/jo0300892
Abstract
The secondary α-deuterium kinetic isotope effect (α-kie) for the solvolysis of (Z)-5-trimethylstannyl 2-adamantyl p-bromobenzenesulfonate in 97% w/w aqueous 2,2,2-trifluoroethanol (97T) at 25 °C has been measured (kH/kD = 1.33). The α-kie is abnormally high compared to the value of 1.23 for the corresponding limiting SN1 solvolysis of 2-adamantyl p-bromobenzenesulfonate, which proceeds via an extended ion-pair mechanism. A novel mechanism for the solvolysis of the tin compound is proposed that accommodates not only the high α-kie but also the absence of internal return.This publication has 24 references indexed in Scilit:
- Tertiary cyclohexyl cations. Definitive evidence for the existence of isomeric structures (hyperconjomers)Journal of the Chemical Society, Perkin Transactions 2, 2001
- The mechanism of solvolysis of 2-adamantyl azoxytosylate: isotopic labelling, medium effect, and attempted deoxygenation studiesCanadian Journal of Chemistry, 1998
- Effects of Bridgehead Metalloidal Substituents (MMe3, M = Si and Sn) on the Stability of the 1-Norbornyl CationJournal of the American Chemical Society, 1996
- Amides. 3. Experimental and Theoretical Studies of the Effect of the Medium on the Rotational Barriers for N,N-Dimethylformamide and N,N-DimethylacetamideJournal of the American Chemical Society, 1995
- Mechanism of solvolysis of 1-(1-adamantyl)ethyl sulfonatesJournal of the American Chemical Society, 1990
- An ab initio molecular orbital study of the 2-adamantyl cationJournal of the American Chemical Society, 1989
- Effects of two oppositely polarizing, distant substituents on the rate and stereochemistry of solvolysis of 2-adamantyl tosylateThe Journal of Organic Chemistry, 1989
- KH/18-Crown-6: A Powerful Base for the Protection of Hindered Alcohols with t-ButyldimethylsilylchlorideSynthetic Communications, 1986
- On the incidence of internal ion pair return during solvolysis of sec-alkyl benzenesulfonatesJournal of the American Chemical Society, 1985
- .alpha.-Deuterium effects on the rates of solvolysis of a 2-adamantyl sulfonate esterJournal of the American Chemical Society, 1971