10502-30-4Relevant articles and documents
Thia-, Aza-, and selena[3.3.1]bicyclononane dichlorides: Rates vs internal nucleophile in anchimeric assistance
Accurso, Adrian A.,Cho, So-Hye,Amin, Asmarah,Potapov, Vladimir A.,Amosova, Svetlana V.,Finn
body text, p. 4392 - 4395 (2011/07/30)
Sulfur-, selenium-, and nitrogen-containing compounds bearing leaving groups in the β-position undergo facile substitution chemistry enabled by anchimeric assistance. Here we provide direct comparisons between such systems in the rigid bicyclo[3.3.1]nonane framework easily derived from 1,5-cyclooctadiene. For a series of dichloride electrophiles of this type, the relative reactivities were found to be Se ? (alkyl)N > S ≥ (propargyl)N > (phenyl)N, with the reaction rates at the two extremes differing by more than 3 orders of magnitude. For the N-alkyl case, substitution rates were largely independent of the trapping nucleophile but were strongly dependent on solvent, showing that the process is controlled by the formation of the high-energy three-membered cationic intermediate.
Transannular Reactions of Cycloalkenes, Cycloalkadienes and Cycloalkatrienes. VIII. The Electrophilic Addition of Pseudohalogenes to Cycloocta-1(Z),5(Z)-diene
Haufe, Guenter,Muehlstaedt, Manfred
, p. 89 - 92 (2007/10/02)
The reaction of cycloocta-1(Z),5(Z)-diene 5 with chlorothiocyanate is described.The main process is the normal anti-addition to produce trans-5-chloro-6-thiocyanato-(Z)-cyclooctene 6.In addition 2,6-dichloro-9-thiabicyclononane 7 and 2,6-dithiocyanato-9-thiabicyclononane 8 are obtained as products of a transannular reaction.
