69912-51-2Relevant academic research and scientific papers
Controlling regiochemistry in negishi carboaluminations. Fine tuning the ligand on zirconium
Lipshutz, Bruce H.,Butler, Tom,Lower, Asher
, p. 15396 - 15398 (2007/10/03)
The species on the zirconocene catalyst is changed from two Cp's to the Brintzinger ligand and catalytic amounts of MAO are used to usually effect a >99% regiocontrol of Negishi carboaluminations of 1-alkynes in toluene. Copyright
Formation of 9,10-unsaturation in the mitomycins: Facile fragmentation of β-alkyl-β-aryl-α-oxo-γ-butyrolactones
Ziegler, Frederick E.,Berlin, Michael Y.,Lee, Kyungae,Looker, Adam R.
, p. 3619 - 3621 (2007/10/03)
(matrix presented) A facile fragmentation of β-alkyl-β-aryl-α-oxo-γ-butyrolactones is reported. A study to assist in the elucidation of the mechanism of the reaction is also revealed.
Comparative investigation of the regioselectivity in styrene and α-methylstyrene hydroalkoxycarbonylation as a function of palladium catalyst structure
Benedek, Csilla,Toroes, Szilard,Heil, Balint
, p. 85 - 93 (2007/10/03)
Catalytic pathways of the styrene and α-methyl-styrene hydroalkoxycarbonylation in the presence of Pd(PPh3)2Cl2 and Pd(PPh3)2Cl2/SnCl2 catalyst precursors have been suggested. As a method, deuterium labelling with EtOD has been applied and it resulted in mixtures of mono- and polydeuterated reaction products, detected and determined by NMR methods. Comparative elucidation of the mechanisms governing these systems does support the assumption that the hydrido route is operative. The different behaviour of the metal-alkyl intermediates accounts for the observed strong influence of catalyst and substrate structure on regioselectivity.
SYNTHESIS AND DECOMPOSITION OF E- AND Z-3,3,5-TRISUBSTITUTED 1,2-DIOXOLANES.
Yoshida,Miura,Nojima,Kusabayashi
, p. 6279 - 6285 (2007/10/02)
The reactions of a number of ozonides and olefins in the presence of boron trifluoride-diethyl ether gave the corresponding mixtures of (E)- and (Z)-1,2-dioxolanes in 12-70% yield. The decomposition of the E-Z isomeric 1,2-dioxolanes 3a-c was undertaken under a variety of conditions, i. e. , thermal, TiCl//4-mediated, FeSO//4-catalyzed, and LiAlH//4-mediated decompositions.
Mechanisms of Elimination Reactions. 36. Stereochemistry and Transition-State Structure in Eliminations from Primary Alkyltrimethylammonium Salts
Tao, Yu-Tai,Saunders, William H.
, p. 3183 - 3188 (2007/10/02)
A study of stereochemistry of elimination in E2 reactions of R1R2CHCHDNMe3+ reveals that syn elimination can become the major reaction path when R1 and R2 are both bulky groups such as aryl or branched alkyl.With OH-/50percent Me2SO-H2O at 80 deg C, the percent of syn is 68.5 for R1 = Ph, R2 = i-Pr; 61.9 for R1 = Ph, R2 = p-MeOPh ; 26,5 for R1 = Ph, R2 = CH3.With n-BuO-/50percent Me2SO-n-BuOH, the percent of syn runs 61.5 for R1 = Ph, R2 = i-Pr; 12 for R1 = n-Bu, R2 = Me; and 1 = n-Bu, R2 = D.The results can be rationalized by a simple conformational argument in which steric interactions between bulky β-substituents and the leaving trimethylammonio group destabilize the trasition state for anti elimination.Primary β-tritium, secondary α-tritium, and primary α-14C isotope effects were determined on the (2,2-diphenylethyl)trimethylammonium ion and compared with similar data on the (2-phenylethyl)trimethylammonium ion, which eliminates by an exclusively anti mechanism.The extent of proton transfer in the transition state seems not to differ widely between the two systems, but the extent of C-N cleavage appears less in the 2,2-diphenylethyl system.Hammett ρ values are smaller in the 2,2-diphenylethyl system, though their interpretation presents ambiguities.
