The Yukawa-Tsuno Relationship in Carbocationic Systems

Institute for Fundamental Research of Organic Chemistry, Kyushu University, Fukuoka, Japan [Pg.267]

Applications of the Yukawa-Tsuno equation 272 Yukawa-Tsuno correlations for benzylic solvolyses generating carbocations 276 Benzylic systems 276 Aryl-assisted solvolyses 295 [Pg.267]

Solvolysis of 1-arylethenyl sulphonates forming vinyl cations 303 Highly electron-deficient carbocation systems 304 Carbocation formation equilibria 315 Triarylmethyl cations 315 Benzhydryl cations 319 1,1-Diarylethyl carbocations 322 [Pg.267]

Yukawa-Tsuno correlations for electrophilic addition of alkenes 322 Hydration of arylalkenes 322 Bromination of arylalkenes 326 [Pg.267]

Structure-reactivity relationship in polyarylcarbocation systems 334 Conformations of carbocations 334 Reactivity-conformation relationship 337 Stabihties of carbocations in the gas phase 343 Structural effects 343 The resonance demand parameter 355 Theoretically optimized strnctnres of carbocations 362 Reaction mechanisms and transition-state shifts 365 Extended selectivity-stability relationships 365 Ground-state electrophilic reactivity of carbocations 366 Sn2 reactions of 1-arylethyl and benzyl precnrsors 372 Concluding remarks 378 Acknowledgements 379 References 379 [Pg.267]