Carbon-13 parameters, configurationally

The Bs are constants indicating how many carbon atoms are attached to the observed C [5 = 1 one adjacent C (i.e., C is CH3) S = 2 C is CH2 S = 3 C is CH S = 4 C is quaternary] and thereby contain a-parameters. For the remaining parameters there are independent sets for each 5 as well. ASM denotes the steric configuration at the adjacent carbon atoms, where M is defined analogously to S for example, A23 signifies a contribution from the methine to the methylene atom under consideration. Consequently, the ASM s replace the p-... 

A parameter that has been useful for defining the anomeric stereochemistry of glycopyranosides is the chemical shift of the anomeric carbon atom, C-l. Similarly, the 13C NMR shifts of C-l in methyl septanosides also diagnostic for their anomeric configuration. In general, the Sc.i values for a-septanosides are slightly upfield (99-104 ppm in completely deprotected septanosides) relative to (S-septanosides (104-111 ppm) (Table I). This distribution of chemical shifts mirrors the trends for pyranosides namely, the C-l chemical shifts for a-pyranosides lie upfield from those of p-pyranosides. This observation suggests that the anomeric effect is operative in... 

Figure 27 shows p(z, t) calculated for BA with the appropriate static and dynamic parameters for BA in the polar aprotic solvent, propylene carbonate. The results show how the charge transfer in Sj occurs. At early times p(z, t) is highly peaked near zero z, where the LE probability is high. As time progresses, the charge transfer occurs and the system approaches the equilibrium configuration (see Section III.A). 

Carboxidation of linear alkenes is presented in Table 7.8 [173]. The location of the C=C bond and configuration of intermediate oxadiazoline complex are two important parameters with these substrates. For terminal alkenes, the complex may have configuration I and II (Figure 7.4). Complex I has the oxygen bound to the first carbon atom, and its decomposition leads to an aldehyde. Complex II has the oxygen bound to the second carbon atom, and its decomposition leads to a ketone. However, decomposition of the latter complex may occur also in a different way, involving... 

---