Allylic substitution overview

Summary Two catalytic reactions, i.e. silylative coupling (mms-silylation) (SC) catalyzed by complexes containing or generating Ru-H and/or Ru-Si bonds (I, II, V, VI) and cross-metathesis (CM) catalyzed by mthenium-carbene (i.e. 1st and 2nd generation mthenium Grubbs catalyst (ID, IV)) of vinyl and allyl-substituted hetero(N,S,B)organic compounds with conunercially available vinyltrisubstituted silanes, siloxanes, and silsesquioxane have been overviewed. They provide a universal route toward the synthesis of well-defined molecular compounds with vinylsilicon functionality. 

In this section, attention is focused on the recent advances and notable applications in the Pd-catalyzed a-substitution reactions of enolates and related derivatives. Although Tsuji-Trost allylations and propagylations are not presented here, an overview of them were already comprehensively discussed and summarized in Chapter V.2.1 of the Handbook of Organopalladium Chemistry fc/r Organic Synthesis [279]... 

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]. 

---