Silicon hydrides reduction

In summary, myriad boron hydride and silicon hydride reduction methods are available for the reduction of indoles to indolines. It is interesting to compare the various methods for the stereoselective reduction of 2,3-dimethylindole to cis- and trfl/is-2,3-dimethylindoline (Table 1). While most methods show a preference for the more stable trans isomer, only with Zn(BH4>2 is this preference pronounced. 

Rahaim, R. J., Jr. Maleczka, R. E., Jr. Pd-Catalyzed silicon hydride reductions of aromatic and aliphatic nitro groups. Org. Lett. 2005, 7, 5087-5090. 

The reaction of thiyl radicals with silicon hydrides (Reaction 8) is the key step of the so-called polariiy-reversal catalysis in the radical chain reduction. The reaction is strongly endothermic and reversible with alkyl-substituted silanes (Reaction 8). For example, the rate constants fcsH arid fcgiH for the couple triethylsilane/ 1-adamantanethiol are 3.2 x 10 and 5.2xlO M s respectively. 

Enantioselective 1,4-reduction of enones can be done using a copper-BINAP catalyst in conjunction with silicon hydride donors.158 Polymethylhydrosilane (PMHS) is one reductants that is used. 

The solid bases CaO and hydroxyapatite catalyze the hydrosilylation of benz-aldehyde by triethoxysilane at 90° in yields of 59% and 72% within one and two hours, respectively.323,324 These reductions also very likely involve activation by valence expansion of the silicon hydride reagent. 

Electron-deficient silicon-centered species, organosilicon hydride reductions,... 

Germanium hydrides (as well as silicon hydrides) can be obtained in high yields by reduction of the corresponding halides or alkoxides by LiAlFLt in the presence of phase-transfer catalysts244. 

Reductions. Silicon hydrides such as 1, which can achieve intramolecular pentacoordination, show enhanced reducing properties. Thus they can reduce aldehydes or ketones to alcohols,1 and reduce carboxylic acids to aldehydes via thermal decomposition of a silyl carboxylate (equation I).2 Reaction of acid chlo-... 

Another reaction type for which EGA catalysis has been thoroughly explored is the reaction between organo-silicon nucleophiles and acetals or unprotected aldehydes and ketones [31-33]. The reaction types are aldol condensation, allyla-tion, cyanation, and hydride reductions depending on which of the nucleophiles (16) to (20) is used. 

The use of free-radical reactions in organic synthesis started with the reduction of functional groups. The purpose of this chapter is to give an overview of the relevance of silanes as efficient and effective sources for facile hydrogen atom transfer by radical chain processes. A number of reviews [1-7] have described some specific areas in detail. Reaction (4.1) represents the reduction of a functional group by silicon hydride which, in order to be a radical chain process, has to be associated with initiation, propagation and termination steps of the radical species. Scheme 4.1 illustrates the insertion of Reaction (4.1) in a radical chain process. 

The reduction of ketones with silicon hydrides has been occasionally performed by radical chemistry for a synthetic purpose. The radical adduct is stabilized by the a-silyloxyl substituent and for RsSi (R = alkyl and/or phenyl) the hydrogen abstraction from the parent silane is much slower than a primary alkyl radical (cf. Chapter 3). On the other hand, (TMS)3SiH undergoes synthetically useful addition to the carbonyl group and the reactions with dialkyl ketones afford yields > 70% under standard experimental conditions, i.e., AIBN, 80-85 °C [45,51]. Reaction (5.25) shows as an example the reduction of 4-tcrt-butyl-... 

As an example, the propagation steps for the reductive alkylation of alkenes are shown in Scheme 7.1. For an efficient chain process, it is important (i) that the RjSi radical reacts faster with RZ (the precursor of radical R ) than with the alkene, and (ii) that the alkyl radical reacts faster with the alkene (to form the adduct radical) than with the silicon hydride. In other words, the intermediates must be disciplined, a term introduced by D. H. R. Barton to indicate the control of radical reactivity [5]. Therefore, a synthetic plan must include the task of considering kinetic data or substituent influence on the selectivity of radicals. The reader should note that the hydrogen donation step controls the radical sequence and that the concentration of silicon hydride often serves as the variable by which the product distribution can be influenced. 

Conjugate reduction. Silicon hydrides and a Pd(0) catalyst reductively cleave allylic acetates selectively (equation I).1... 

Asymmetric reduction of alkyl aryl ketones with trialkoxysilanes is promoted by a catalytic amount of chiral nucleophiles [39]. The reactive species is a transiently prepared hypervalent silicon hydride. 2, 4, 6 -Trimethylacetophenone was reduced with equimolecular amounts of trimethoxysilane in the presence of the monolithio salt of (R)-BINAPHTHOL (substrate Li=20 l) in a 30 1 ether-TMEDA mixed solvent at 0 °C to afford the R product in 90% ee (Scheme 21) [40]. The presence of TMEDA was crucial to achieve high yield and enantiose-lectivity. Reduction of less hindered ketonic substrates preferentially gave the... 

---