Catalytic reactions hydrosilylation

The hydrosi(ly)lations of alkenes and alkynes are very important catalytic processes for the synthesis of alkyl- and alkenyl-silanes, respectively, which can be further transformed into aldehydes, ketones or alcohols by estabhshed stoichiometric organic transformations, or used as nucleophiles in cross-coupling reactions. Hydrosilylation is also used for the derivatisation of Si containing polymers. The drawbacks of the most widespread hydrosilylation catalysts [the Speier s system, H PtCl/PrOH, and Karstedt s complex [Pt2(divinyl-disiloxane)3] include the formation of side-products, in addition to the desired anh-Markovnikov Si-H addition product. In the hydrosilylation of alkynes, formation of di-silanes (by competing further reaction of the product alkenyl-silane) and of geometrical isomers (a-isomer from the Markovnikov addition and Z-p and -P from the anh-Markovnikov addition. Scheme 2.6) are also possible. 

The hydrosilylation of carbonyl compounds by EtjSiH catalysed by the copper NHC complexes 65 and 66-67 constitutes a convenient method for the direct synthesis of silyl-protected alcohols (silyl ethers). The catalysts can be generated in situ from the corresponding imidazolium salts, base and CuCl or [Cu(MeCN) ]X", respectively. The catalytic reactions usually occur at room tanperature in THE with very good conversions and exhibit good functional group tolerance. Complex 66, which is more active than 65, allows the reactions to be run under lower silane loadings and is preferred for the hydrosilylation of hindered ketones. The wide scope of application of the copper catalyst [dialkyl-, arylalkyl-ketones, aldehydes (even enoUsable) and esters] is evident from some examples compiled in Table 2.3 [51-53],... 

Rh colloids were isolated during the hydrosilylation of trimethy(vinyl)silane with triethoxysilane using RhCl3 in EtOH as pre-catalyst. The colour changes observed during the catalytic reaction (from yellow, to red and black) are due to the formation of colloids as demonstrated by TEM this fact was in agreement with the catalytic activity behaviour observed [14]. 

Asymmetric hydrosilylation can be extended to 1,3-diynes for the synthesis of optically active allenes, which are of great importance in organic synthesis, and few synthetic methods are known for their asymmetric synthesis with chiral catalysts. Catalytic asymmetric hydrosilylation of butadiynes provides a possible way to optically allenes, though the selectivity and scope of this reaction are relatively low. A chiral rhodium complex coordinated with (2S,4S)-PPM turned out to be the best catalyst for the asymmetric hydrosilylation of butadiyne to give an allene of 22% ee (Scheme 3-20) [59]. 

Asymmetric hydrosilylation of ketones has developed enormously since these early reports and probably there are few catalytic reactions for which the variety in ligand structure is so immense as for this reaction. Numerous reports have been published and in general oxazoline-based ligand systems seem to give the highest enantioselectivities. In the following we will mention a few... 

On the other hand, alkenal 14a is selectively formed with recovery of Rh4(GO)i2 under CO pressure (20 atm) in a stoichiometric reaction mole ratio = Rh4(GO)i2 13 Me2PhSiH = 1 4 4 as well as a catalytic reaction. When 13 and Me2PhSiH are mixed at once in a GDGI3 solution of Rh4(GO)i2 under CO atmosphere, 14a is smoothly formed as a major product with concomitant formation of small amounts of 15 and Me2PhSiOH. In the case that 13 and Me2PhSiH are added separately, it is critical to add 13 to a solution of Me2PhSiH and Rh4(CO)i2 for the production of 14a. Reverse addition results in hydrosilylation of 13 only. Similar results are observed in the silylformylation catalyzed by Rh2(pfb)4. ... 

Insertion of unsaturated molecules into a transition metal-silyl bond has been suggested for the catalytic reactions related to hydrosilylation and silylcarbonylation. However, there is little direct evidence supporting such a process for unsaturated molecules to insert into a metal-silyl bond in organometallic complexes. " Thus, the fact that 108 is readily derived from 11 and 13 demonstrates the participation of this process in the catalytic cycle of silylformylation. 

The third part of this chapter reviews previously described catalytic asymmetric reactions that can be promoted by chiral lanthanoid complexes. Transformations such as Diels-Alder reactions, Mukaiyama aldol reactions, several types of reductions, Michael addition reactions, hydrosilylations, and hydroaminations proceed under asymmetric catalysis in the presence of chiral lanthanoid complexes. 

In the previous chapters we discussed alkene-based homogeneous catalytic reactions such as hydrocarboxylation, hydroformylation, and polymerization. In this chapter we discuss a number of other homogeneous catalytic reactions where an alkene is one of the basic raw materials. The reactions that fall under this category are many. Some of the industrially important ones are isomerization, hydrogenation, di-, tri-, and oligomerization, metathesis, hydrocyana-tion, hydrosilylation, C-C coupling, and cyclopropanation. We have encountered most of the basic mechanistic steps involved in these reactions before. Insertions, carbenes, metallocycles, and p -allyl complexes are especially important for some of the reactions that we are about to discuss. 

The performance of this ligand class in different catalytic reactions depends not only on the individual reaction, but also on the metal used. The rhodium NHC complex in Figure 4.23 catalyses the hydrosilylation of acetophenone with 98% conversion and... 

As pointed out in the introduction, a particular feature of hydrosilylation reactions is that they require catalysis. Arguably the most valuable of enantioselective synthetic methods are those in which asymmetric induction occurs from small quantities of enantiomerically pure catalysts. It is natural, therefore, that considerable effort has been directed towards the catalytic enantioselective hydrosilylation-oxidation of C —C double bonds. Some degree of success has been met in the hydrosilylation of simple alkenes and 1,3-dienes, and in intramolecular hydrosilyla-tions. Also, as discussed at end of this section, a catalytic enantioselective disilylation (effectively the same as a hydrosilylation) has been developed for a,)3-unsaturated ketones. 

Ravlov, V. A Mechanism of Asymmetric Induction in Catalytic Hydrogenation, Hydrosilylation, and Cross-Coupling Reactions on Metal Complexes, Russ. Chem. Rev. 2002, 71, 39-56. 

Rhodium-Catalyzed Asymmetric Hydrosilylation of Ketones. Complex 2 is a good catalyst for catalytic asymmetric hydrosilylation of ketones (eq 7). The reactions are carried out by using 1-naphthylphenylsilane at -40 °C in THF in the presence of 2 (1 mol%) for 3-4 days. Several types of ketones are hydrosilylated to afford optically active alcohols after acidic work-up. 

This chapter presents the hydrosilylation processes as well as the main types of reactions related to hydrosilylation (except double silylation) in which intermediates with metal-silicon bonds (i. e., silicometallics vs. organometallics) play a decisive role with mechanistic implications for both new and well-known catalytic reactions leading to formation of organosilicon compounds [6]. Double silylation (bissilylation) of unsaturated organic compounds has recently been reviewed comprehensively [7]. 

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