D. A. Evans Carbonyl Addition Reactions-2 Chem 206 Explain the following observations The Proton-Silicon Correlation +○c三N 1-4 addition with their proton counterparts but with an attendant greater exothermicity i Organosilanes undergo a range of thermal rearrangements processes in direct analogy with their proton counterparts TMSCN 1-2 addition k(S=106K(H TMSO CN A J. Ashe Ill. JACS 1970. 92. 1233 OSiMe. heat c Colvin, pp 37-8 th Truesdale Grimm, Nesbitt, JAcs1975,97,3229 JAcS1977.99.5009 OTMS Si transfer is intramolecular etal,JAcS1974.96,4283 Non-catalyzed processes may also occur if a proper geometry for atom transfer can be achieved oc1976.41 Me3Sc式N→-CN-SMe3 MS Organosilicon hydrides undergo transition metal catalyzed hydrosilylation processes in direct analogy with normal hydrogenation reactions H RO-P RO OR H-SIRa Me H-H Me 8/-8~m RhO catalysis Rh(o catalysis Hydrosilylation of C-C Bonds". T. Hayashi In Comprehensive Asymmetric Catalysis, Jacobsen, E.N. Pfaltz, A and Yamamoto, H Editors; Springer Verlag eidelberg, 1999; Vol L, 319-332D. A. Evans Carbonyl Addition Reactions-2 Chem 206 Explain the following observations O O + C N OH OH CN THF/H2O O TMSO CN TMSCN O O + benzene C N 1-4 addition 1-2 addition R1 R2 OSiMe3 SR RS– ZnI2 R1 R2 SR SR with Truesdale, Grimm, Nesbitt, JACS 1975, 97, 3229 JACS 1977, 99, 5009 Me3Si SR R1 R2 O + Me3Si OEt O N2 R H O CN– or F– OEt O N2 R OTMS 1-5 min with Truesdale, Grimm JOC 1976, 41, 3335 R H O O TMS RO P OR + R P O O RO OR SiR3 R P OTMS O RO OR with Hurst, Takacs JACS 1978, 100, 3467 Non-catalyzed processes may also occur if a proper geometry for atom transfer can be achieved R O P O R OR TMSO RO R OTMS P O RO RO "The Proton–Silicon Correlation" ■ Organosilanes undergo carbonyl addition processes in direct analogy with their proton counterparts but with an attendant greater exothermicity. ■ Organosilanes undergo a range of thermal rearrangements processes in direct analogy with their proton counterparts. X H X H k(Si) =10+6 K(H) A. J. Ashe III, JACS 1970. 92, 1233 O O Me3Si O Me MeMe Me C O O SiMe3 O Me Me Me Me heat Colvin, pp 37-8 ■ Organosilicon hydrides undergo transition metal catalyzed hydrosilylation processes in direct analogy with normal hydrogenation reactions R N O SiR3 SiR3 R N O SiR3 SiR3 Yoder et al., JACS 1974. 96, 4283 DG* 15-22kcal/mol Si transfer is intramolecular Me3Si C N C N SiMe3 rt H–SiR3 H–H R Me R Me H R Me SiR3 Rh(I) catalysis Rh(I) catalysis "Hydrosilylation of C–C Bonds". T. Hayashi In Comprehensive Asymmetric Catalysis, Jacobsen, E. N.; Pfaltz, A.; and Yamamoto, H. Editors; Springer Verlag: Heidelberg, 1999; Vol I, 319-332