Silane Carbanions

Lithium silylamides react smoothly with tiifluoronitrosomethane to give diazenes Traces ot water initiate the decomposition of the latter with liberation of a trifluoromethyl carbanion, which is trapped by carbonyl compounds [775] (equation 116) Desilylation of trialkyl(trifluoromethyl)silanes by fluoride ion produces also a trifluoromethyl carbanion, which adds to carbonyl carbon atoms [136, 137] (equations 117 and 118)... 

The novel cyclizadon takes places by the silane-mediated condensadon of nitroarenes with allylic carbanions, in which a sLx-membered nitrogen-containing ting is constnicted fEq. 9.54. ... 

In Entry 5, the carbanion-stabilizing ability of the sulfonyl group enables lithiation and is then reductively removed after alkylation. The reagent in Entry 6 is prepared by dilithiation of allyl hydrosulfide using n-bulyl lithium. After nucleophilic addition and S-alkylation, a masked aldehyde is present in the form of a vinyl thioether. Entry 7 uses the epoxidation of a vinyl silane to form a 7-hydroxy aldehyde masked as a cyclic acetal. Entries 8 and 9 use nucleophilic cuprate reagents to introduce alkyl groups containing aldehydes masked as acetals. 

Alternatively, some conclusions can be derived from the relative reactivities of car-banions. For example, DePuy and colleagues13 made use of a clever method involving reactions of silanes with hydroxide ion to deduce acidities of such weak acids as alkanes and ethylene. The silane reacts with hydroxide ion to form a pentacoordinate anion that ejects a carbanion held as a complex with the hydroxysilane rapid proton transfer gives the stable silanoxide ion and the carbon acid (equation 5). 

As with the silanes, some of the most useful synthetic procedures involve electrophilic attack on alkenyl and allylic stannanes. The stannanes are considerably more reactive than the corresponding silanes because there is more anionic character on carbon in the C—Sn bond and it is a weaker bond.103 104 There are also useful synthetic procedures in which organotin compounds act as carbanion donors in palladium-catalyzed reactions, as discussed in Section 8.2.3 Organotin compounds are also very important in free-radical reactions, which will be discussed in Chapter 10. 

The intramolecular addition of carbon nucleophiles to alkenes has received comparatively little attention relative to heterocyclization reactions. The first examples of Pd-catalyzed oxidative carbocyclization reactions were described by Backvall and coworkers [164-166]. Conjugaled dienes with appended al-lyl silane and stabilized carbanion nucleophiles undergo 1,4-carbochlorination (Eq. 36) and carboacetoxylation (Eq. 37), respectively. The former reaction employs BQ as the stoichiometric oxidant, whereas the latter uses O2. The authors do not describe efforts to use molecular oxygen in the reaction with allyl silanes however, BQ was cited as being imsuccessful in the reaction with stabihzed car-banions. Benzoquinone is known to activate Ti-allyl-Pd intermediates toward nucleophilic attack (see below. Sect. 4.4). In the absence of BQ, -hydride eUm-ination occurs to form diene 43 in competition with attack of acetate on the intermediate jr-allyl-Pd" species to form the 1,4-addition product 44. 

The carbomagnesiation of vinyisiianes is a powerful method for the generation of synthetically useful a-silyl carbanions. However, simple vinyisiianes such as trimethyl(vinyl) silane do not undergo carbometalation with Grignard reagents (Scheme 59) °. In early days, only limited success had been achieved by using perfluorovinylsilanes °°. 

Addition to aldehydes or ketones of a-sulfinyl carbanions or of a-lithio-silanes (Peterson)... 

Another point which needs to be clarified from the start is the nomenclature of metalated silanes We will frequently use the term silyl anion in this chapter when we talk about metalated silanes. Although the term anion defines, literally taken, an ionic compound, this expression, when used by us, does not necessarily imply that the compound in question is of ionic nature, but covers, as well, in analogy to the use of the term carbanion , silicon compounds with a polarized covalent silicon-metal bond. 

The [4 + 2] cycloaddition of a-phenylselenopropenoyl trimethylsilane (75) with 2,3-dimethylbuta-1,3-diene is unusual in that a significant portion of product mixture consists of the hetero-Diels-Alder dihydropyran adduct 76. The phenylselenenyl substituent appears to be responsible for this unusual pattern of reactivity, since propenoyl trimethylsilane gives only the expected regioisomer (77, X = H) (Scheme 116)14. a-Selenenyl substituted a,/l-unsaturated acyl silanes such as 75 were used to prepare a series of substituted dienes in excellent yields through the addition of a-sulphinyl carbanions, Brook rearrangement and expulsion of sulphinate, in a reaction pathway recognisably more typical of acyl silanes (Scheme 117). 

The reactive species in fluoride-mediated carbon-carbon bond-forming reactions has been investigated.146 The regio- and diastereo-selectivities of silanes reacting with cyclohexenone in the presence of a catalytic amount of fluoride have been compared with the reactivity of analogous solvent-separated lithium ion pairs. Closely analogous behaviour has been observed, showing that carbanions and not siliconate complexes are the reactive species in the fluoride-catalysed reactions. 

In 1968 Peterson published his results about the reaction of a-silylated carbanions with carbonyl compounds to achieve /3-hydroxyalkyl-silanes. He found that instantaneous elimination affords unsaturated hydrocarbons ( Peterson olefmation )180 Thus, the lithiated trimethyl-benzyl-silane (274) plus benzophenone (135) give via lithium l,l,2,-triphenyl-2-TMS-ethanolate (275) 1,1,2-triphenyl-ethene (276)180 ... 

The mechanism involves the preferential attack of the hydride on the less hindered silicon with formation of a pentacoordinated anionic species which collapses to give an a-silyl carbanion intermediate and SiH4 gas. The a-silyl carbanion may then take up a hydrogen from the hydrogen source (e.g., silane or solvent) to yield 7 or may lose... 

Several authors have demonstrated the feasibility of the alkylation of a MSMA substrate to obtain the homologous RSMA via reaction of the corresponding a-silylcarbanion with an alkyl halide. Treatment with LDA of (allyl)(pyrrazolylmethyl) silane gives a carbanion that on trapping with methyl iodide, leads to the unique formation of the corresponding RSMA derivative without traces of compounds that could have resulted from the allylic system. However, when. v-butyllithium is used instead of LDA, partial methylation of this system also occurs.66... 

The introduction of vinylsilyl end groups into a polymer chain has been achieved by several techniques. Since vinylsilyl functions are sensitive to the attack by strong nucleophiles 27), it was considered appropriate to decrease the nucleophilicity of the styryl carbanions by the addition of oxirane before reacting them with either chloromethyldimethylvinylsilane or chlorodimethylvinyl silane 28a). The following structures are formed ... 

By itself, the Brook rearrangement is not very useful but, if the carbanion can do something else other than just get protonated, something useful may happen. We have seen what happens to the epoxides of vinyl silanes. Dihydroxylation of the same alkenes also gives interesting chemistry when the diols are treated with base. 

Masked carbanions, such as silanes, also react with isatins at position 3 and this methodology has been applied to the synthesis of 1,3-oxathiolanes440 441 (Scheme 102). 

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