Substrate , effects reactions

Xenon difluoride [4, 5, 7, 8,10] is a white crystalline material obtained through the combination of fluorine and xenon m the presence of light The reagent is commercially available and possesses a relatively long shelf-life when stored cold (freezer) Xenon difluoride is very effective for small-scale fluormation of alkenes and activated nucleophilic substrates. The reactions are usually conducted between 0 °C and room temperature in chloroform or methylene chloride solutions Hydrogen fluoride catalysis is sometimes helpful Xenon difluoride reacts in a manner that usually involves some complexation between the substrate and reagent followed by the formation of radical and radical cation intermediates... 

The variation of enantioselectivities with temperature and pressure was investigated. The effects of these two factors are very substrate dependent and difficult to generalize even in a single substrate serie. However, it seems that enantioselectivities are shghly better at 25-40 °C than at lower temperatures (0 °C or less). The stereoselectivity can be inverted for specific alkenes (formation of the S or R enantiomer preferentially). For several substrates, the reactions tend to proceed to completion with optimal ee s when performed at lower hydrogen pressure (2 bar) instead of 50 bar (Fig. 13). Pronoimced variation of enantioselectivities with hydrogen concentration in solution may indicate the presence of two (or even more) different mechanisms which happen to give opposite enantiomers for some substrates. 

SN1 Very strong effect reaction favored by polar solvents Weak effect reaction favored by good nucleophile/weak base Strong effect reaction favored by good leaving group Strong effect reaction favored by 3°, allylic, and benzylic substrates... 

Simple Pd salts and complexes which contain neither phosphines nor any other deliberately added ligands are well known to provide catalytic activity in cross-coupling reactions. Such catalytic systems (often referred to as ligand-free catalysts ) often require the use of water as a component of the reaction medium.17 In the majority of cases such systems are applicable to electrophiles easily undergoing the oxidative addition (aryl iodides and activated bromides), although there are examples of effective reactions with unactivated substrates (electron-rich aiyl bromides, and some aryl chlorides).18,470... 

The C-H insertion of acetals generates protected forms of /3-ketoesters, as illustrated in Equation (22).83 Effective reactions were possible with aryl, vinyl, and alkynyl ketals, but ketals of saturated aldehydes were not viable substrates. 

Terminal alkyne Id affords 2d, albeit with somewhat lower chemical yield, irrespective of which catalyst was employed. A distinct difference between the two catalysts is observed with the trialkylsilyl-substituted alkyne le. An excellent chemical yield is obtained when [RhCl(CO)2]2 is employed, but the substrate is unreactive with [RhCl(CO)dppp]2. Moreover, Wilkinson catalyst activated by AgOTf is unable to catalyze the PK reaction with this substrate effectively. 

Overall, while the combinations of substrate effects, ambient NOz levels, and other gas-particle phenomena preclude a definitive answer, the formation of significant amounts of nitroarenes in heterogeneous particle-phase N02-PAH, atmospheric reactions seems unlikely, e.g., much slower than photooxidation or ozonolysis. This conclusion also applies to heterogeneous reactions of N205 with particle-bound PAHs on diesel and wood soot (Kamens and co-workers, 1990 see also Pitts et al., 1985c, 1985d, 1985e). 

Substrate concentration is yet another variable that must be clearly defined. The hyperbolic relationship between substrate concentration ([S ) and reaction velocity, for simple enzyme-based systems, is well known (Figure C1.1.1). At very low substrate concentrations ([S] ATm), there is a linear first-order dependence of reaction velocity on substrate concentration. At very high substrate concentrations ([S] A m), the reaction velocity is essentially independent of substrate concentration. Reaction velocities at intermediate substrate concentrations ([S] A"m) are mixed-order with respect to the concentration of substrate. If an assay is based on initial velocity measurements, then the defined substrate concentration may fall within any of these ranges and still provide a quantitative estimate of total enzyme activity (see Equation Cl. 1.5). The essential point is that a single substrate concentration must be used for all calibration and test-sample assays. In most cases, assays are designed such that [S] A m, where small deviations in substrate concentration will have a minimal effect on reaction rate, and where accurate initial velocity measurements are typically easier to obtain. 

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