Alkylation titanocene-catalyzed

It should be noted that titanocene-catalyzed carbosilylation of alkenes and dienes, which uses alkyl halides and chlorosilanes, involves alkyl radical addition to styrenes and dienes [68]. The reaction uses butylmagnesiumchloride and a catalytic amount of titanocene dichloride, which would form the complex... 

Titanocene dichloride catalyzes the reduction of alkyl, aryl, and vinyl bromides, aryl chlorides, alkoxy- and halosilanes ketones, esters, and carboxylic acids with alkyl Grignard reagents. This Cp2TiCl2/RMgX system can also be used for the hydromagnesation of alkynes, dienes, and alkenes (Section 3.2.5). Kambe et al. have reported a new type of titanocene-catalyzed transformation with vinyl Grignard reagents and chlorosilanes to furnish l,4-disilyl-2-butenes, as shown in Scheme 3.43 [31]. 

Titanocene-catalyzed Double Alkylation or Double Silylation of Styrenes... 

Tab. 3.23 Titanocene-catalyzed double alkylation of olefins with alkyl bromides...

Tab. 3.24 Titanocene-catalyzed carbosilylation using alkyl halides and chlorosilanes...

Titanocene- and zirconocene-catalyzed alkene polymerization involves initial alkyl group transfer from alkylaluminum cocatalyst to Ti or Zr centers and subsequent multiple insertion of monomer into the metal-carbon bond. Zr complex catalyzed carbomagnesation shown in Eq. 5.33 [128-136] also involves alkyl ligand transfer between the main group metal and Zr. 

Transition metal-catalyzed hydroboration of carbon-carbon multiple bonds using organoborane derivatives and coupling with alkanes to form linear alkyl-boranes has provided valuable applications in organic synthesis.Titanocene catecholborane complexes recently synthesized and characterized by Hartwig also appear to be the best examples of genuine / -BH a complexes (Figure 13.3). ... 

Assisted Metallations of Unsaturated Hydrocarbons. Titanocenes and zir-conocenes catalyze the addition of M—R (M = B, Mg, Al R = H, alkyl) bonds across C=C double bonds. The bydroboration of olefins (eq. 40) is believed to involve the species Cp2Ti(BH4)2 (252). 

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