Donor silyl

The ability to promote /S elimination and the electron-donor capacity of the /3-metalloid substituents can be exploited in a very useful way in synthetic chemistry. Vinylstannanes and vinylsilanes react readily with electrophiles. The resulting intermediates then undergo elimination of the stannyl or silyl substituent, so that the net effect is replacement of the stannyl or silyl group by the electrophile. An example is the replacement of a trimethylsilyl substituent by an acetyl group by reaction with acetyl chloride. 

Some electrophile-nucleophile reactions are guided more by orbital interactions than by electrostatics. The key interaction involves the donor orbital on the nucleophile, i.e., the highest-occupied molecular orbital (HOMO). Examine the HOMO of enamine, silyl enol ether, lithium enolate and enol. Which atom is most nucleophilic, i.e., which site would produce the best orbital overlap with an electrophile ... 

A high degree of syn selectivity can be obtained from the addition of enamines to nitroalkenes. In this case, the syn selectivity is largely independent of the geometry of the acceptor, as well as the donor, double bond. Next in terms of selectivity, are the addition of enolates. However, whether one obtains syn or anti selectivity is dependent on both the geometry of the acceptor and the enolate double bond, whereas anti selectivity of a modest and unreliable level is obtained by reaction of enol silyl ethers with nitroalkenes under Lewis acid catalysis. 

The cyclohcxadicnc 84 is a good H donor but the cyclohcxadicnyl radical 85 is slow to react and fragments to provide the silyl radical 86 which initiates polymerization. The reported transfer constant for 84 in styrene polymerization at 80 °C is very low (0.00045).ni>... 

Very recently, even examples of donor-stabilized bissilylene complexes have been introduced. For instance, the two cyclic systems 13 and 14 are prepared by an aminolysis reaction of the respective bis(chloro)silyl complexes. The x-ray structure analysis of 13 has been performed [39]. 

Weiss et al. (1984) showed that A V-bis-silylated anilines react in aprotic dichloro-methane with generation of diazonium salts and formation of the non-nucleophilic hexamethyldisiloxane (Scheme 2-28). The authors indicate that the monosilylated aniline C6H5NHSi(CH3)3 reacts in many cases in an analogous way. This seems surprising, since the hydroxytrimethylsilane HOSi(CH3)3 that is formed is a potential proton donor, as it will rapidly condense to give (CH3)3SiOSi(CH3)3 + H20. 

Alkali metal derivatives of 2-(trimethylsilyl)aminopyridines can be further derivatized by insertion of 1,3-dicyclohexylcarbodiimide. Functionalized guani-dinates are formed in this reaction via a 1,3-silyl shift. Scheme 170 illustrates the reaction sequence as well as the preparation of an aluminum complex of the modified ligand, which exhibits pseudo jS-diketiminate binding of the metal center, thus exemplifying the coordinative versatility of this new multi-N-donor system. ... 

There seem to be few applications for which the use of weaX "silyl donors" is either necessary or desirable. Other imwrtant considerations for the selection of the correct reagents for a particular application are summarized in. Table 8.15. The strongest silylating reagent of all is a mixture of TMSIM-BSTFA-TNCS (1 1 1). 

A titanium catalyst 20 that incorporates binaphthyl chirality along with imine and phenolic (salen) donors is highly active in addition of silyl ketene acetals to aldehydes.160... 

The trimethylsilyl group can be replaced by a dialkylsilyloxy group, in which case the silyl ether serves as the hydride donor. 

Copper-catalyzed systems have been developed that reduce ketones directly to silyl ethers. The reactions involve chiral biphenyl diphosphine type ligands and silane or siloxane hydride donors.187... 

Especially noteworthy is the relative large shielding for the 31P nucleus in the 31P NMR spectra of 15, which is quite unusual for two-coordinate phosphorus. Evidently, the latter is caused by the strong o--donor ability of the silyl and germyl groups, which is also reflected in the calcu-... 

Scheme 6 a Incorporation of a silyl-spaced dimer into DNA, and treatment of the DNA strand with fluoride furnished DNA strand containing a dimer-unit with an open backbone. b Schematic representation of the light (ho) induced excess electron transfer (ET) from the reduced flavin to the dimer, followed by cycloreversion (CR). c The five DNA duplexes 13-17 containing the flavin donor and the dimer acceptor at increasing distances, together with the measured repair yields after irradiation for 1 min... 

The thermal [1] or photochemical [5] isomerization of N-silylated allylamine in the presence of Fe(CO)5 provides the corresponding N-silylated enamines 7a and 7b. Z-enamine 7b does not react in any of the examined cycloadditions. The cyclopropanation of E-enamine 7a with methyl diazoacetate under copper(I) catalysis provides the donor-acceptor-substituted cyclopropane 9 [1], which can be converted in good yield into the interesting dipeptide 10 [6]. 

Enantioselective protonation of silyl enol ethers using a SnCl4-BINOL system has been developed (Scheme 83). 45 This Lewis-acid-assisted chiral Bronsted acid (LBA) is a highly effective chiral proton donor. In further studies, combined use of a catalytic amount of SnCl4, a BINOL derivative, and a stoichiometric amount of an achiral proton source is found to be effective for the reaction.346 347... 

Enol silyl ethers (ESE) as electron donors 199 Ketones as electron acceptors 212 Electron transfer as the unifying theme 218... 

The wide diversity of the foregoing reactions with electron-poor acceptors (which include cationic and neutral electrophiles as well as strong and weak one-electron oxidants) points to enol silyl ethers as electron donors in general. Indeed, we will show how the electron-transfer paradigm can be applied to the various reactions of enol silyl ethers listed above in which the donor/acceptor pair leads to a variety of reactive intermediates including cation radicals, anion radicals, radicals, etc. that govern the product distribution. Moreover, the modulation of ion-pair (cation radical and anion radical) dynamics by solvent and added salt allows control of the competing pathways to achieve the desired selectivity (see below). 

The notion of enol silyl ethers (ESE) as electron donors was first provided by Gassman and Bottorff,34 who showed that selective (carbonyl) deprotection can be readily achieved in the presence of an alkyl silyl ether group via an electron-transfer activation (e.g., equation 9). 

These authors also noted that the electron-donor ability of various derivatives of 2,2-dimesityl-1-phenylethenol decreases in the order enolate > enol > enol silyl ether > enol phosphate > enol acetate. As such, a simple derivatization allows the ready modulation of the electron-donor properties of ends. 

Electron donor/acceptor organization of enol silyl ethers... 

Having shown that the enol silyl ethers are effective electron donors for the [D, A] complex formation with various electron acceptors, let us now examine the electron-transfer activation (thermal and photochemical) of the donor/ acceptor complexes of tetranitromethane and quinones with enol silyl ethers for nitration and oxidative addition, respectively, via ion radicals as critical reactive intermediates. 

Comments on the thermal nitration of enol silyl ethers with TNM. The strikingly similar color changes that accompany the photochemical and thermal nitration of various enol silyl ethers in Table 2 indicates that the preequilibrium [D, A] complex in equation (15) is common to both processes. Moreover, the formation of the same a-nitroketones from the thermal and photochemical nitrations suggests that intermediates leading to thermal nitration are similar to those derived from photochemical nitration. Accordingly, the differences in the qualitative rates of thermal nitrations are best reconciled on the basis of the donor strengths of various ESEs toward TNM as a weak oxidant in the rate-limiting dissociative thermal electron transfer (kET), as described in Scheme 4.40... 

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