Hydrofunctionalization of olefins

Radicaloid insertions of olefins into the Rh H bond of [Rh (TPP)(H)] has been used to obtain Rh —CH2—(alkyl)—Nu// species (NuH = OH, NH) using olefins functionalized with end-on —OH and —NH functionalities. Under basic conditions, intramolecular SN2-type attack of the Nu at the a-carbon atom of Rh —CH2—(alkyl)—Nu yields [Rh (TPP)] and cyclic organic products (—CH2—(alkyl)—Nu—) (see Fig. 47). Protonation of [Rh TPP)] then allows regeneration of [Rh° (TPP)(H)]. The combination of these reactions constitutes a new method for selective intramolecular anti-Markovnikov hydrofunctionalization of olefins with O—H and N—H functionalities (150). In this way, three-and five-membered ring compounds (epoxides, furan derivatives, pyrrolidine derivatives) were readily obtained. Formation of four- or six-membered rings... 

The co-dimerization of ethylene with olefins has also been studied extensively and has been called hydrovinylation. A seminal example, discovered by Bogdanovic and Wilke, involved the co-dimerization of ethylene and norbornene catalyzed by a (TT-aUyl)nickel catalyst (Equation 22.34). This chemistry and more modem versions of these additions of one olefin C-H bond across another were presented in Chapter 16 on the hydrofunctionalization of olefins. 

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