Alkenes reaction with chlorotrimethylsilane

The Cg reactant used for step (vii) was synthesised from lithio-1-heptyne by reaction with oxirane foiiowed by catalytic reduction to the Z-alkene, non-3-enol, and conversion to the 1-iodide by reaction with chlorotrimethylsilane in acetonitrile containing lithium iodide. 

Fiirstner reported the first McMurry-type reactions working with 5-10 mol% of titanium trichloride and stoichiometric amounts of zinc powder in the presence of chlorotrimethylsilane. The amount of TiCl3 could be reduced to 2 mol% when (ClMe2SiCH2)2 was used as a reagent [125, 131]. At the same time, Burton and coworkers reported atom transfer radical additions of perfluoroalkyl iodides 39 to alkenes 40 catalyzed by 20 mol% of a low-valent titanium compound generated from TiCLt and zinc powder affording 41 in 10-85% yield (Fig. 13). A tandem radical addition/5-exo cyclization/iodine transfer reaction with diallyl ether proceeded in 66% yield [132]. 

Synthesis and Reaction Chemistry of a,p-Unsaturated Acyl Complexes Derived from (2). Two methods for the preparation of optically active ( )- and (Z)-a,p-unsaturated iron acyls from (2) have been reported." One method involves aldol condensation of (2) with aldehydes followed by 0-methylation to produce diastereomeric acyls (18). This mixture (18) is then treated with Sodium Hydride to produce predominantly ( )-a,p-unsaturated acyl complexes (19) (eq 13). Alternatively, (2) can be depro-tonated and treated with Chlorotrimethylsilane to produce the C-silylated complex which is subsequently deprotonated and treated with an aldehyde. This Peterson alkenation produced mixtures... 

The pioneering studies in this area were reported in 1999 by Narasaka, who demonstrated intramolecular heteroatom Heck-type reactions of 0-pentafluorobenzoyl oximes [97]. As shown below, treatment of unsaturated substrate 97 with a catalytic amount of Pd(PPh,y in the presence of triethyl amine provided pyrrole 98 upon workup with chlorotrimethylsilane. The mechanism of this reaction proceeds via oxidative addition of the N—O bond to afford 99, which undergoes alkene insertion into the Pd—N bond to provide alkyl-palladium complex 100. The exo-methylene product 101 is generated by [i-hydride elimination from 100, and isomerization to the desired pyrrole 98 occurs when chlorotrimethylsilane is added. 

Alkyl alkanoates are reduced only at very negative potentials so that preparative scale experiments at mercury or lead cathodes are not successful. Phenyl alkanoates afford 30-36% yields of the alkan-l-ol under acid conditions [148]. Preparative scale reduction of methyl alkanoates is best achieved at a magnesium cathode in tetrahydrofuran containing tm-butanol as proton donor. The reaction is carried out in an undivided cell with a sacrificial magnesium anode and affords the alkan-l-ol in good yields [151]. In the absence of a proton donor and in the presence of chlorotrimethylsilane, acyloin derivatives 30 arc formed in a process related to the acyloin condensation of esters using sodium in xylene [152], Radical-anions formed initially can be trapped by intramolecular addition to an alkene function in substrates such as 31 to give aiicyclic products [151]. 

The additions of tellurium tetrahalides to olefins in the presence of alcohols proceed equally well when the tetrahalides are generated in the reaction mixture from tellurium dioxide and chlorotrimethylsilane in methanoP or concentrated hydrochloric acid/methanol. trans-2-Methoxycyclohexyl tellurium trichloride was obtained in this manner in quantitative yield . In the reactions of terminal alkenes, the TeCl3 group (from TeO and concentrated hydrochloric acid) added according to the Markovnikov rule producing 2-alkoxy-1 -alkyl tellurium trichlorides. The trichlorides were not isolated but were reduced with disodium disulfite to the ditellurium compounds, which, in turn, were converted to the tellurium trichlorides by treatment with sulfuryl chlorides. For data on these tellurium trichlorides see p. 316. The overall yields range from 15 to 70%. 

Shibasaki et al. developed a method for the direct synthesis of chlorohydrins or 2-acetoxy alcohols from disubstituted olefins [41). Various kinds of chlorohydrins are prepared from the corresponding alkenes with bis(trimethylsilyl)peroxide (BTSP) and chlorotrimethylsilane (TMSCl) in the presence of the catalyst (SnCU or (SnO) ). It is worth noting that 2-acetoxy alcohols could be obtained under similar reaction conditions using trimethylsilyl acetate (TMSOAc) instead of TMSCl with the promotion of Zr(0 Pr)4 in place of SnCU (Scheme 10.20). 

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