Heteroatom-containing

In the absence of heteroatom containing substituents (e.g. halo-, cyano-), at or conjugated with the radical center, carbon-centered radicals have nucleophilic character. Thus, simple alkyl radicals generally show higher reactivity toward electron-deficient monomers (eg. acrylic monomers) than towards electron-rich monomers (e.g, VAc, S) - Table 3.6. 

The regioselectivity observed in these reactions can be correlated with the resonance structure shown in Fig. 2. The reaction with electron-rich or electron-poor alkynes leads to intermediates which are the expected on the basis of polarity matching. In Fig. 2 is represented the reaction with an ynone leading to a metalacycle intermediate (formal [4C+2S] cycloadduct) which produces the final products after a reductive elimination and subsequent isomerisation. Also, these reactions can proceed under photochemical conditions. Thus, Campos, Rodriguez et al. reported the cycloaddition reactions of iminocarbene complexes and alkynes [57,58], alkenes [57] and heteroatom-containing double bonds to give 2Ff-pyrrole, 1-pyrroline and triazoline derivatives, respectively [59]. 

A hydrogen-bond basicity scale has been developed that can be used to determine the relative basicity of molecules. Table 8.2 gives the p hb values for several common heteroatom containing molecules. This is obtained from the protonated form (conjugated acid) of the base in question. The larger the number, the more basic is that compound. 

Fig. 14 The heteroatom-containing 1,3-diradicals, where the triplet stabilization is depressed by the strengthening of p-Jt -q (denoted by bold lines) and weakening of p-JC-q wavy lines) interaction path...

Kielbasinski, P. and Mikoiajczyk, M. (2007) Chiral Heteroatom-containing Compounds, in Future Directions in Biocatalysis (ed. T.Matsuda), Elsevier, pp. 159-203. 

An interesting extension of the above reactions in the achiral series is the facile, regioselective, one-pot bicyclization of aminodialkenes leading to a variety of polycyclic heteroatom-containing skeletons (Eq. 4.25) [137]. 

McElroy, N. R., Jurs, P. C. Prediction of aqueous solubility of heteroatom-containing organic compounds from molecular structure. J. Chem. Inf. Comput. Sd. 2001, 41,1237-1247. 

Six-membered heterocycles have also been extensively used to mimic the central pyrazole scaffold of limonabant (382). Merck and Co. has utilised pyiidines (510) [314], and pyrimidines (511) [315] in this capacity. Sanofi-Aventis has also claimed a series of pyridine-based analogues [316], as exemplified by (512) and additionally the non-heteroatom containing terphenyl (513) [317]. 

Rieger et al. described a heteroatom-containing C, symmetric metallocene 13 whose stereoselectivity depended on the activator [28, 29], The resulting PP contained fewer stereoerrors when activated with a combination of TiBA and trityl tetrakis(pentafluorophenyl)borate than with MAO. In addition, the molecular weight was lower with MAO. To explain this, it was proposed that some of the stereoerrors arise by reversible chain transfer to aluminum. 

An enantioselective imino-ene reaction was developed by Lectka to provide ct-amino acid derivatives.27 Aryl alkenes (cr-methyl styrene, tetralene), aliphatic alkenes (methylene cyclohexane), and heteroatom-containing enes, all gave high yields and high ee s of the homoallylic amides (Equation (17)). The mechanism of this reaction has been proposed to proceed through a concerted pathway. This mechanism is evidenced by a large kinetic isotope effect observed in the transfer of H(D). 

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