Reversal of diastereoselectivities in intra- and intermolecular reactions of 2-adamantanylidenes primarily caused by electron-donating and electron- withdrawing substituents on C5

[reaction: see text] A reversal of diastereoselectivity was observed for novel 5-(trimethylsilyl)adamantan-2-ylidene (1c) with regard to 5-hydroxyadamantan-2-ylidene (1a). Ostensibly in intermolecular reactions, 5-substituted 2-adamantanylidenes (1) are sterically unbiased. However, inductive effects originating from the pendant group bend the divalent carbon bridge of 1 either toward (ERG's, e.g., -Si(CH(3))(3)) or away from (EWG's, e.g., -OH) the gamma-position. Hence, the more exposed side is more susceptible to intermolecular reaction and the other side concomitantly undergoes intramolecular 1,3-CH insertions more readily.     

Fluxional behavior of a cadmium zwitterion complex: proton transport and tautomerism in methylene chloride solution

The synthesis and structure of the tautomeric Cd(II) isoindoline zwitterion coordination compound [Cd(4'-MeLH)(NO(3))(2)].CH(3)OH (4'-MeLH = 1,3-bis[2-(4-methylpyridyl)imino]isoindoline) are reported. In methylene chloride solution, tautomer interconversion occurs as the N-H proton moves between the identical imine nitrogen atoms. We report the kinetics of proton transfer as followed by variable temperature (1)H NMR spectroscopy and demonstrate that methanol of solvation and adventitious water facilitate rapid proton transfer.     

Evaluation of the two-dimensional reversed-phase-reversed-phase separations of low-molecular mass polystyrenes

The resolving power of four reversed-phase-reversed-phase two-dimensional (2D) chromatographic systems was evaluated using information theory (IT) and a geometric approach to factor analysis. The first separation dimension employed a C18 column, while the second separation dimension employed a carbon clad zirconia column. Mobile phases in each dimension were either methanol or acetonitrile. The sample matrix that was employed in this study contained a mixture of 58 components, comprised of stereoisomers and structural isomers of a systematic variation in molecular weight. Each of the components were oligostyrenes, with between two and five configurational repeating units having either n-butyl, sec-butyl or tert-butyl end groups. In the two-dimensional systems employed in this study, between 46 and 49 of the 58 components could be separated, depending on the mobile phase combinations--with apparent resolution that could not possibly be achieved in a single one-dimensional separation. The results from this study indicate that in order to fully evaluate the resolving power of a 2D system multiple methods of analysis that evaluate the separation potential are most appropriate. This becomes increasingly important when the sample contains components that are very closely related and the retention of solutes displays a high degree of solute crowding.     

Studies on high-temperature amination reactions of aromatic chlorides using discrete Palladium-N-Heterocyclic Carbene (NHC) complexes and in situ palladium/imidazolium salt protocols

The palladium catalysed coupling of aryl chlorides and amines can be readily achieved with short reaction times when carried out at high temperatures under thermal or microwave conditions. These coupling protocols are successful using two co-ordinate palladium-N-heterocyclic carbene complexes, or imidazolium salt protocols.     

Loops and the Lagrange Property

Let $\cal F$ be a family of finite loops closed under subloops and factor loops. Then every loop in $\cal F$ has the strong Lagrange property if and only if every simple loop in $\cal F$ has the weak Lagrange property. We exhibit several such families, and indicate how the Lagrange property enters into the problem of existence of finite simple loops.     

Specializations of Brauer classes over algebraic function fields

Let be either a number field or a field finitely generated of transcendence degree over a Hilbertian field of characteristic 0, let be the rational function field in one variable over , and let . It is known that there exist infinitely many such that the specialization induces a specialization , where has exponent equal to that of . Now let be a finite extension of and let . We give sufficient conditions on and for there to exist infinitely many such that the specialization has an extension to inducing a specialization , the residue field of , where has exponent equal to that of . We also give examples to show that, in general, such need not exist.