Tributylstannane tributyltin

In a 50 ml flask fitted with a reflux condenser 5.5 g (0.0189 mol) of tributylstannane (tributyltin hydride) is added to 3.5g (0.018mol) of octyl bromide. An exothermic reaction ensues. Cooling is applied if the temperature rises above 50°. After 1 hour the mixture is distilled, giving 80% yield of octane and 90% yield of tributyltin bromide. 

Another hydride used successfully for the same purpose is tributylstannane (tributyltin hydride) in ether, tetrahydrofuran or acetonitrile. Triethylsilane acts similarly, but more slowly and more selectively it does not reduce nitro groups (equation 96). ... 

The indolyltributylstannanes, which are more robust than their trimethylstannyl counterparts, are prepared similarly [166, 167]. Labadie and Teng synthesized the IV-Me, N-Boc, and jV-SEM (indol-2-yl)tributylstannanes [167], and Beak prepared the A-Boc trimethyl- and tributyltin derivatives in high yield [166]. Caddick and Joshi found that tributylstannyl radical reacts with 2-tosylindoles to give the corresponding indole tin compounds as illustrated [168]. 

Alternative desulfurizations can be achieved using tributylstannane or hydrazine. Reaction with the former reagent is carried out by heating the mercaptole for 1.5 hours at 80° with 3-4 equivalents of tributylstannane and azobis(isobutyronitrile) as a catalyst and distilling the product and the byproduct, bis(tributyltin) sulfide, in vacuo. Yields are 74-95% [798],... 

The 1,2-hydrostannylation of (2-iodobenzyl)vinylsilanes 146 with tributylstannane induced with AIBN followed by elimination of tributyltin iodide provides 2,5-dihydro-benzo[f]siloles 147 (R =R = Me, R =R = vinyl, R = R = allyl, R = Me, R = allyl) together with minor amounts of benzosilacyclohexenes 148 or benzosilacyclo-heptene 149 <2002JOC8906>. 

A parallel trend is observed for MgBr2-promoted additions of cis- and trans-crotyl tributylstannanes to a-benzyloxy aldehydes but the effect is much smaller (Table 9) [18], In such reactions the orientation of the allylic stannane and the chelated aldehyde is governed by steric effects in which the vinylic y-hydrogen orients over the five-membered chelate (Fig. 4). Support for this picture is provided by competition experiments in which y3,)8-dimethylallyl tributyltin was found to be markedly slower than the crotyl or allyl derivatives in additions to a-benzyloxypropanal. The observed rate decrease was attributed to the disfavored relationship of a vinylic methyl substituent with the chelate ring resulting in unfavorable steric interactions. 

The tributyltin enolates 74 are readily prepared from the corresponding enol acetates and tributyltin methoxide in the absence of solvent [34]. The tin enolates thus obtained occur in the 0-Sn form and/or the C-Sn form, and both species can be used for the aldol reaction of this system. Although the tin enolates themselves have adequate reactivity toward aldehydes [34c], in the presence of the BINAP silver(I) catalyst the reaction proceeds much faster even at -20 °C. Optimum conditions entail the use of THF as solvent and the results employing these conditions in the catalytic enan-tioselective aldol reaction of a variety of tributyltin enolates with typical aromatic, a,/3-unsaturated, and aliphatic aldehydes are summarized in Table 2. TTie characteristic features are (i) All reactions proceed to furnish the corresponding aldol adducts 75 in moderate to high yield in the presence of 10 mol % (i )-BINAP AgOTf complex at -20 °C for 8 h, and no dehydrated aldol adduct is observed (ii) with an a,j3-unsaturated aldehyde, the 1,2-addition reaction takes place exclusively (entry 3) (iii) a bulky alkyl substituent of tin enolate increases the enantioselectivity of the aldol reaction. For instance, the highest ee (95 % ee) is obtained when the tin enolate prepared from pinacolone 77 or rert-butyl ethyl ketone 79 is added to aldehydes (entries 2, 7, and 8) (iv) addition of the cyclohexanone-derived enol tributylstannane 78 (( )-... 

In reduction of arenediazonium fluoroborate with tributylstannane, formation of the arene takes place not only by hydrogen atom abstraction from the stannane, but also by reaction of the radical interm iate with the solvent. Reduction of 4-methoxybenzenediazonium fluoroborate with tributyltin deuteride in te-trahydrofuran or acetonitrile affords not only deuterated but also deuterium-free arenes (equation 89). There are also small amounts of biphenyl by-products. ... 

But before 1980, the foundations for essentially all modern synthetic radical reactions had been laid, sometimes by synthetic organic chemists but more often by physical organic chemists. Kharasch reactions (now often called atom transfer reactions) were known since the 1930s and 1940s, and tributyltin hydride was introduced in the 1960s. In the 1970s, SnAc reactions and redox chain aromatic substitutions (Minisci reactions) were already topical, and allylations with allyl-tributylstannane were first described. In short, there were a number of ways to generate and trap radicals on the one hand, and a number of fundamental transformations of radicals such as addition and cyclization to multiple bonds on the... 

BioMeT TBTF BRN 4125568 Caswell No. 867C EINECS 217-847-9 EPA Pesticide Chemical Code 083112 Fluorotributylstannane NSC 179737 NSC 195319 Stannane, fluorotributyl- Stannane, tributylfluoro- Tri-n-butylstannyl fluoride Tin, tributyl-, fluoride Tin, tributylfluoro- Tributylfluorostannane Tributylstannane fluoride Tributyltin fluoride. Antifoulant used in marine paints. Registered by EPA as a fungicide (cancelled). Crystals mp n 270° (dec). Elf Atochem N. Am. Fluka. 

Trifluoromethyl)tributylstannane is readily prepared by the reaction of bis(tributyltin)... 

Tributyltin hydride adds to terminal acetylenes in the presence of triethylborane to give mixtures of E)- and (Z)- alkenes, in which the tin atom is attached to C(l), e.g. equation 40215,216 reverse regiochemistry is observed in the reaction of tributylstannane with terminal acetylenes in the presence of rhodium complexes, e.g. [RhCl (1,5-cyclooctadiene)]2, to yield exclusively the adducts 297. ... 

For transformations based on stannane-mediated radical chain sequences, selenol esters are the precursors of choice owing to their ease of preparation, stabilities, and ability to accomplish Sh2 reactions (see Sect. 3.2.1). However, replacing the selenol esters by thiol esters in these tributyltin hydride- or allyl-tributylstannane-mediated chain reactions would be attractive from a synthetic viewpoint. 

Acetyloxy)tributylstannane, lOCl, 90. Tributyltin acetate. Acetato-0)tributylstannane [56-36-0]... 

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