Kinetic isotope effect in hydrogen isotope exchange between diphenylphosphine and methanol or 2-methylpropane-2-thiol in aprotic solvents

Author(s):  
Andrzej Wawer ◽  
Iwona Wawer
2011 ◽  
Vol 75 (10) ◽  
pp. 2696-2707 ◽  
Author(s):  
Yunyan Ni ◽  
Qisheng Ma ◽  
Geoffrey S. Ellis ◽  
Jinxing Dai ◽  
Barry Katz ◽  
...  

1975 ◽  
Vol 53 (1) ◽  
pp. 26-40 ◽  
Author(s):  
Nick Henry Werstiuk

Methyl exo-2-bromo-1-norobornanecarboxylate-endo,endo-5,6-d2 (1b) has been prepared and solvolyzed at 112° in 80:20 EtOH-H2O buffered with NaOAc. The loss of 85–90% of the deuterium available on the front face of 1b in the formation of the tricyclic ester 6D coupled with a novel analysis established that the endo:exo preference for 1,3 elimination is at least 15:1 to 20:1. A comparison of the solvolytic kinetic isotope effect (1.18 ± 0.04) for 1b and the 1,3-elimination kinetic isotope effect (1.45–1.6) with data for 1,2 eliminations indicates that elimination occurs from the classical, perhaps 1,3 hyperconjugatively stabilized carbocation 20. The endo:exo preference established in this study is used to reinterpret 1,3-elimination data determined by Collins in the solvolysis of deuteriohydroxyphenyl norbornyl tosylates.


2013 ◽  
Vol 78 (23) ◽  
pp. 12029-12039 ◽  
Author(s):  
Lori I. Robins ◽  
Kristen M. Meisenheimer ◽  
Emily J. Fogle ◽  
Cory A. Chaplan ◽  
Richard L. Redman ◽  
...  

Sign in / Sign up

Export Citation Format

Share Document