Rhodium-catalyzed hydroformylation overview

Because of the immense importance of phosphites as ligands, not only in rhodium-catalyzed hydroformylation, several recent reviews have dealt with these compounds and provided quite complete collections of individuals [2, 15], In contrast to these overviews, in this chapter we will focus on some issues that are seldom in the focus. This concerns the synthesis of alcohols that are required as the alcohol component for the synthesis of phosphorous acid triesters. This has never been considered in detail. However, their availability is an important criterion for chemists dealing with large-scale applications and therefore has economic consequences. Some general synthesis protocols of phosphites together with some typical examples will also be considered. The complexation behavior of phosphites with rhodium will also be discussed briefly. Some remarks about the stability of ligands and Rh catalysts will close this chapter. 

Myrcene is a very abundant acyclic monoterpene available from the essential oils of various plants including wild thyme and hops. Recently, an excellent overview on the manufacture and transformation of this natural product was given by Behr and Johnen [125]. Commercially, myrcene is produced by the pyrolysis of pinenes [126]. The rhodium-catalyzed hydroformylation of myrcene gives usually a mixture of fragrance aldehydes in more than 90% combined yields (Scheme 6.37) [127, 128]. The main aldehyde, which accounted for 70 - 80% of the mass balance, results from the reaction with the less substituted C=C bond through the formation of a T) -allyl rhodium intermediate complex [127]. The reaction was also performed in a toluene/water biphasic system using the water-soluble TPPTS ligand and a cationic surfactant [84]. 

---