Regioselectivity defined

Silylmethylation of fullerenes can be achieved by Grignard reaction of Cjq with Me2Si(0 Pr)MgCl (Scheme 3.4). Two different types of silylmethylated 1,2-fullerene adducts are formed [8]. The use of different solvents leads either to the 1,2-product 12 or to the unprecedented 1,4-addition product 13. These compounds react easily with various alcohols or phenols, which makes silylmethylated fullerenes a versatile starting material for regioselectively defined fullerene compounds [10]. Some examples are shown in Scheme 3.4. 

Note that the terms regiose lective and regiospeafic however are defined in terms of each other A re giospecific reaction is one that IS 100% regioselective... 

A valuable feature of the Nin/Crn-mediated Nozaki-Takai-Hiyama-Kishi coupling of vinyl iodides and aldehydes is that the stereochemistry of the vinyl iodide partner is reflected in the allylic alcohol coupling product, at least when disubstituted or trans tri-substituted vinyl iodides are employed.68 It is, therefore, imperative that the trans vinyl iodide stereochemistry in 159 be rigorously defined. Of the various ways in which this objective could be achieved, a regioselective syn addition of the Zr-H bond of Schwartz s reagent (Cp2ZrHCl) to the alkyne function in 165, followed by exposure of the resulting vinylzirconium species to iodine, seemed to constitute a distinctly direct solution to this important problem. Alkyne 165 could conceivably be derived in short order from compound 166, the projected product of an asymmetric crotylboration of achiral aldehyde 168. 

A related situation is found in the case of P-substituted cycloketones here, the electronic difference between the two a-carbons is almost insignificant, resulting in unselective migration upon chemical oxidation. BVMOs have a particularly different behavior, as they can influence the stereo- and/or regioselectivity of the biooxidation. In the latter case, the distribution of proximal and distal lactones is affected by directing the oxygen insertion process either into the bond close or remote to the position of the P-substituent. Consequently, a regioisomeric excess (re) can be defined for this biotransformation, similar to enantiomeric excess or diastereomeric excess values [143]. 

In the Heck reactions discussed above it was essential to use polar aprotic solvents such as acetonitrile or DMF if high regioselectivity was to be achieved. In other Heck couplings the use of water as a solvent has recently gained attention. The advantages of water compared with standard organic solvents are many - it is, for example, cheap and nontoxic - but its usefulness extends only over a number of well-defined applications, partly because of problems with the solubility of the reactants and catalysts. The development of aqueous catalytic systems is, consequently, an important field [21]. 

A systematic exploration of the intramolecular [4+2]/[3+2] cycloaddition cascade of 1,3,4-oxadiazoles was described. The studies permit the use of unsymmetrical dienophiles, dipolarophiles, and oxadiazoles as well as to control the cycloaddition regioselectivity and diastereoselectivity. The scope and utility of the reaction were defined <2006JA10589>. The tandem intramolecular [4+2]/[3+2] cycloaddition cascade reaction of 1,3,4-oxadiazole was applied to the syntheses of a series of natural products including a total synthesis of (-)- and ent-(+)-vindoline <2006JA10596>. 

One of the most defining characteristics of the late metal a-diimine polymerization systems is the uniquely branched polyolefins that they afford. This arises from facile p-hydride elimination that late transition metal alkyl complexes undergo. The characteristics of the isomerization process have been the subject of much investigation, particularly with the more easily studied Pd(II) a-diimine system. The process is initiated by P-hydride elimination from the unsaturated alkyl agostic complex 1.17, followed by hydride reinsertion into olefin hydride intermediate 1.18 in a non-regioselective manner (Scheme 5). In doing so, the metal center may migrate... 

The nature and distribution of the products of the dimerization or oligomerization of unsymmetrical olefins, such as propene, will depend, among others, on the direction of addition of the hydrido- and alkylnickel species to the olefin, i.e., on the regioselectivity of the catalyst (see Section 1 V,E). In order to define the direction of addition of hydrido- or alkylnickel species to terminal olefins, we shall adopt the convention nickel-to-C, addition [Eq. (12)] (Ni —> Cj) ... 

Based on the orbital approximations, it is clear that/(r) is the DFT analog of the frontier orbital regioselectivity for nucleophilic (f (r)) and electrophilic (/ (r)) attack. It is then reasonable to define a reactivity indicator for radical attack by analogy to the corresponding orbital indicator,... 

The synthesis of libraries of structurally defined compounds can potentially be achieved either by split-mix synthesis or by parallel synthesis of individual compounds. The synthesis requires a reliable methodology of oligosaccharide synthesis, where stereochemistry and regioselectivity have to be achieved unlike other library approaches. Development of synthetic methodologies that can provide access to any oligosaccharide structure is underway. 

Advanced characterization of the structure, properties and function of the self-assembled precursor can be extrapolated from studies on the more robust crosslinked material, especially in changing or challenging environments, in which the assemblies would not remain intact. The introduction of crosslinks has aided in the maintenance of native conformations as a powerful technique during studies to determine the order and structure of biological assemblies [61, 62], Moreover, the robust characteristics that the crosslinks provide, combined with the ability to define their regioselectivity, are expected to expand the realm of possible applications for nanoscale materials. 

The previous section has described how one can compute accurately a system of about 30 atoms including one transition metal. The problem is, as mentioned above, that these are usually not the real catalysts, but model systems where the bulky substituents have been replaced by hydrogen atoms. Calculations on model systems are usually at least indicative of the nature and the energy barriers of the steps involved in a catalytic cycle, but they are often unable to provide information on some of the most interesting features, namely enantioselectivity and regioselectivity. The reason for this failure is simply that selectivity is often associated to the presence of the bulky substituents which are deleted when defining the model system. 

More recently, Coates et al. reported well-defined cobalt complexes with high catalytic activity and regioselectivity [25-27]. The key concept for the... 

Unsymmetrical epoxides (39) can form two isomers, (40) and (41), on reaction with nitrate anion and so raise the issue of regioselectivity. Under acidic conditions terminal epoxides are found to predominantly yield the primary nitrate ester (41) although this is not clear cut and propylene oxide is reported to yield an ill defined mixture of isomers. A comprehensive study on the regioselectivity of epoxide opening with nitrate anion under acidic conditions was conducted on glycidol. ... 

In order to keep polyamides soluble in relatively apolar solvents, the use of flexible (macro)monomers such as a, co-(diaminopropyl)polydimethylsiloxane [52] or oligoethyleneglycol-based diamines [53, 54] has been proven to be a successful approach (Fig. 10). Poly condensations of dimethyl adipate with a variety of diamines were successful in bulk and at moderate temperatures between 60 and 100 °C (reaction A in Fig. 10). The low temperatures (60-100 °C) that suffice in these polymerizations also allow the use of monomers that are thermally instable, such as diethyl fumarate [53]. Moreover, multifunctional amines could be regioselectively polymerized up to molecular weights of 9 kDa, making lipase catalysts a valuable tool for the preparation of well-defined polyamides that can be further functionalized with active groups. 

This classification, defined in Table 13 with examples, appears very clear and logical in view of the standard classification of isomers. However, the historical development followed a rather curious course. The term constitutional selectivity, unfortunately a somewhat clumsy word which is rarely used, appeared in the literature as late as 1979 -2. This was after an inspiring, but not completely clear, discourse by Hassner on the almost equivalent term regioselectivity which greatly appealed to chemists and was immediately accepted. It is important to note that the now universally accepted definition of stereoselectivity and its subclasses enantio- and diastercoselectivity did not appear in print until as late as 19714. Before that, the term stereoselectivity apparently had the special meaning of the present term diastereoselectivity5. One consequence of this was discussed in the previous section. Furthermore, in the past, the terms selectivity and specificity were usually coupled. The latter term will be discussed in Section 1.2.3.3, but it is currently regarded with suspicion and best avoided. 

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