Stannylenes 3-effect

Bu3Sn)20 BzCl. The use of microwaves accelerates this reaction. Bu2Sn(OMe)2 is reported to work better than Bu2SnO in the monoprotection of diols. The monoprotection of diols at the more hindered position can be accomplished through the stannylene if the reaction is quenched with PhMe2SiCl (45-77% yield).Microwave heating has been found to be effective for this transformation in some cases. ... 

The second point is certainly the most important as seen in the case of the stannylenes (Chapter 4) while the first point needs some further discussion. The electron-releasing substituent may act via a simple inductive cr-efFect (A) or via a mesomeric jx-effect (B), or via both effects. 

As heavier analogs of carbenes141) stannylenes can be used as ligands in transition-metal chemistry. The stability of carbene complexes is often explained by a synergetic c,7t-effect cr-donation from the lone electron pair of the carbon atom to the metal is compensated by a a-backdonation from filled orbitals of the metal to the empty p-orbital of the carbon atom. This concept cannot be transferred to stannylene complexes. Stannylenes are poor p-a-acceptors no base-stabilized stannylene (SnX2 B, B = electron donor) has ever been found to lose its base when coordinated with a transition metal (M - SnXj B). Up to now, stannylene complexes of transition metals were only synthesized starting from stable monomoleeular stannylenes. Divalent tin compounds are nevertheless efficient cr-donors as may be deduced from the displacement reactions (17)-(20) which open convenient routes to stannylene complexes. 

The formation of betaines in the reaction of silylenes (germylenes, stannylenes) Me2E14 (E14 = Si, Ge, Sn) with ylides H2C=E15Me3 (E15 = P, As) under gas-phase conditions occurs without a barrier as a strongly exothermic process. The thermal effects of the reactions are presented in Table XVII. 

The following set of oxides provides a useful series of six-rings for comparison of substituent effects. Where R = R and is bulky, six-membered rings are planar (6a) as in (f-Bu2GeO)3 formed above65 and the Sn analogues66 with R = f-Bu or r-amyl. The stannylene Ar(f)2Sn, discussed later, readily forms a similar cyclic oxide67 and use of a... 

Monoalkylation of a vic-glycol.1 Selective monoalkylation or monoacylation of the vic-glycol group of dimethyl L-tartrate is possible by conversion to the O-stannylene acetal (1) by reaction with dibutyltin oxide. The acetal is converted selectively to a mono derivative (3) by reaction with an alkyl halide or acyl chloride (excess) and CsF (about 2 equiv.). KF or Bu4NF are less effective than CsF. 

The structures of some stable stannylenes, such as several amino-, " alkoxy-, and arylthio-substituted intermediates, have been revealed by X-ray crystallography. They are monomeric crystals and the tin atom has the coordination number 2. The divalent tin in such compounds is stabilized by the effects of electronegativity of the ligand atoms and by the donation of the lone-pair electrons to the vacant 5p orbital of the tin. Although the first monomeric dialkyl- and diaryl- stannylenes in... 

Tokitoh and co-workers further succeeded in the synthesis of overcrowded diarylstannylenes, Tbt(Tcp)Sn (170 Tcp = 2,4,6-tricyclohexylphenyl) and Tbt (Tpp)Sn [171 Tpp = 2, 4,6-tris(l-ethylpropyl)phenyl], by the exhaustive desulfurization of the corresponding tetrathiastannolanes with a trivalent phosphine reagent (Scheme 14.74). Since only a few convenient precursors have been available for the generation of stannylenes, this new method should provide us with a useful synthetic route for a variety of overcrowded stannylenes. The successful synthesis of a series of Tbt-substituted diarylstannylenes enabled the systematic comparison of their electronic absorptions with those of the previously reported overcrowded diarylstannylenes, which led to the elucidation of the substituent effect on the n—transition of stannylenes. 

Selectivity can be an overriding commodity in cases where reactivity is dictated by logic and accepted concepts. Such is the case with stannylene acetals of diols and trialkyl-stannyl ethers of alcohols. Enhanced nucleophilicity of oxygen attached to tin and well-documented stereoelectrorric effects associated with methine carbon atoms of trialkyhin ethers lead to remarkably selective reactions of (7-substitution and oxidation in polyhydroxy compounds. 

The nature of substituent effects on the position of absorption maxima corresponding to n — p transition in polyatomic silylenes have been considered in detail in theoretical studies of Apeloig and coworkers126 128. Unfortunately, there is no similar study for germylenes, stannylenes or plumbylenes. However, the available experimental data show that the main conclusions obtained by Apeloig and coworkers are also applicable to polyatomic germylenes, stannylenes and plumbylenes. 

Me3C6H)2, E(Si(SiMe3)3)(2,4,6-(CF3)3C6H2), E(NR2)2, E(PR2)2. None of these series is complete. Obviously, the same substituents reveal their effects to a different extent, depending on the nature of the divalent atom. Unfortunately, there are no UV data on labile stannylenes and plumbylenes with relatively simple substituents. 

When the two oxygen atoms involved in the stannylene acetal are diaste-reotopic, three dimers, two with C2 symmetry, can be formed, as shown in Fig. 7 for those obtained from 1,2-propanediol. Dimers are named by means of the numbers of the tricoordinate oxygen atoms.44 Steric effects appear to be the most important factor in determining the relative populations of the three dimers. In particular, stannylene acetals derived from fram-diols with one adjacent axial substituent exist in solution, to the level of detection of 119Sn NMR spectroscopy, as the symmetric dimer in which the tricoordinate oxygen atom is not adjacent to the axial substituent.44 Similarly, dialkylstannylene acetals from carbohydrate-derived terminal 1,2-diols exist predominantly as symmetric dimers with the primary oxygen atoms tricoordinate (Fig. 8).19,37... 

Alkylation requires more vigorous conditions. These reactions were originally performed on the stannylene acetal with the alkylating reagent in DMF at elevated temperatures (45°C for methyl iodide or 100°C for benzyl bromide)66 or on the tributylstannyl ether in neat benzyl bromide or allyl bromide at 80-90°C.67 It was then discovered that the presence of added nucleophiles markedly accelerates the reactions, so that alkylation of both tributylstannyl ethers and dibutylstannylene acetals in benzene, which is very slow at reflux with benzyl bromide alone, occurs at a reasonable speed at reflux in the presence of added tetrabutylammonium halides.57,63 Many other nucleophiles are also effective, including A-methylimidazole68 and... 

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