Trimethyltin hydride

The organotin hydrides are easily identified by their infrared spectra which contain very strong Sn—H absorptions in the 1800-1880 cm.-1 region. Tri-n-butyltin hydride, trimethyltin hydride, and dimethyltin dihydride are colorless liquids with respective boiling points 65-67°C./0.6 mm., 59°C./760 mm.,... 

Trimethyltin hydride has been shown to add to trimethylvinyltin, and triethyltin hydride to triethylvinyltin, to give both the 1,1- and the 1,2-distannylethanes, whereas triphenyltin hydride reacts with triphenyl vinyltin to give only the 1,2-adduct (180). 

Trimethyltin chloride reacts with carboxylic acids at 100° to give the corresponding chloride carboxylates Me2Sn(Cl)OCOR (187, 188), and diethyltin dihydride, triethyltin hydride, hexaethylditin, and bis(triethyltin) oxide have been shown to react with lead tetraacetate to give diethyltin diacetate or triethyltin acetate, as appropriate (189). 

Phosphine and lithium aluminium hydride form lithium tetra-phosphinoaluminate (15) which reacts with trimethyltin chloride to give the phosphine (16). 

Finally, Podoplelov and coworkers41 have prepared trimethyltin hydride and benzyltrimethyltin labelled with tin-117 from a tin sample enriched to 92% in 117Sn. The photochemical reaction between dibenzyl ketone and trimethyltin-117 hydride was used to investigate the chemically induced dynamic nuclear polarization of tin-containing radicals. 

Radical homologation. This tin pinacolate is known to generate trimethyltin radicals at 60° and appears to be superior to tributyltin hydride as a source of stannyl radicals for addition of alkyl halides to O-benzylformaldoxime (equation I).1 Iodides, bromides, and selenides can be used as radical precursors. The same... 

Trimethyltin hydride adds mainly 1,2 to piperylene, but a variety of other organotin compounds are also formed. This suggests that the reaction may be a radical addition (IS). 

B. Tributyltin, Trimethyltin and Triphenyltin Hydride (Bu3SnH, Me3SnH,... 

Examples of halide reduction chemistry include the BU3 SnH-mediated reduction of iodide (41) en route to clavepictine A and B reported by Momose and coworkers64 (equation 17) as well as the reduction of iodide (42) during Danishefsky s work towards the synthesis of epothilone A (equation 18)73. Herzog and Roewer demonstrated that trimethyltin hydride can be used to effect the reduction of halooligosilanes to the corresponding silane in the presence of a Lewis base such as triphenylphosphine (equation 19)77, while Crich and Mo reported the beneficial effect of catalytic benzeneselenol during the BU3 SnH-mediated reduction and fragmentation of bromo-/) -lactones (43) (equation 20)94. 

With the exception that — 80°C. traps (Dry Ice-acetone) are used instead of the — 126°C. traps, this synthesis is accomplished as detailed above in Sec. C. From 14.9 g. (0.075 mole) of trimethyltin chloride and 10.0 g. (0.26 mole) of sodium boro-hydride, an 11.4-g. (0.069-mole, 92%) sample of a colorless liquid product was obtained. The product was identified as trimethyltin hydride from its gas-phase infrared spectrum 14 from its boiling point, 58°C./752 mm., literature,2 59°C./760 mm. and from its refractive index, n 1.4472, literature,2 1.4484. 

Trimethyltin dimethylamide reacts with transition-metal hydrides to give such products as > -CpCr(CO)3SnMe3, >j -CpMo(CO)2SnMe3 and >j -Cp(CO)3WSnMe3 with the evolution of Me,NH. ... 

The addition of trimethyltin hydride to (- )-menthyl (ii)-2,3-diphenylpropenoate under free radical conditions leads to a mixture of all four possible diastereomers, two of them being in higher proportion. One of the major diastereomers, after isolation by column chromatography, has been reduced to chiral 2,3-diphenyl-3-trimethylstannylpropanol22. 

Salt-like trimethyl tin sodium is obtained from trimethyltin hydride with Na in liq... 

Trimethyltin hydride oxidatively adds to a number of osmium complexes to produce the Os(SnMe3)2H2(CO)(PPh3)2 ... 

Trimethyltin hydride reacts with [PtR2(dppm)] by oxidative addition and loss of alkane at RT when R = Me or Et the corresponding phenyl complex requires heating to 50°C ... 

A clean separation between the homolytic and heterolytic processes can be achieved with trimethyltin hydride and methyl propiolate.87 In the dark at 50 °C, with acetonitrile as solvent, and galvinoxyl present as a radical inhibitor, only methyl 2-trimethyl-stannylacrylate is formed, but at 60 °C in cyclohexane, with AIBN as a radical initiator, a 4 1 mixture of methyl Z- and E-2-trimethylstannylacrylate is obtained (equation 4-49). 

The yields are essentially quantitative and the distannanes can often be used without purification. When Pd(PPh3)4 is added portionwise to trimethyltin hydride, the reaction is exothermic, and the hydride boils under reflux (equation 18-24). Tributyltin hydride reacts similarly, and the reaction of (solid) triphenyltin hydride can be carried out in benzene. The reaction with a 1 1 molar mixture of McvSnH and Bu3SnH gives Me3SnSnMe3, Me3SnSnBu3, and Bu3SnSnBu3 in the ratio of 1 2 1. 

In the same study as claims for SnH, Birchall and Manivannan also reported that the " Sn chemical shift for a purported SnMe ion was 5 322. This material was prepared by the reaction of trimethyltin hydride with fluorosulfonic acid. At the time (1985), this value could be considered unusually deshielded, so that this species clearly had at least some stannylium ion character. No further structural data, however, were available. 

Tin hydride reduction has been utilized to introduce tritium at C28 of dihydrocalysterol. " When (23R,24R,2diR)- or (23/ ,24/ ,285 )-28-bromo-23,28-cyclostigmast-5-en-3)3-ol (12) was mixed with trimethyltin chloride and treated with [ H]-sodium borohydride, formation of a C-T bond giving 13 took place. 

Other activating groups y to the cyclopropane ring and in allylic position to the C-C double bond include the trimethyltin, bis(methylsulfanyl) acetal, gj.yj i538.2069 cyano, tricarbonyliron, carboxy, acyloxy, and hydroxy moieties. Enamines with a cyclopropyl group attached to the /J carbon atom undergo the same transformation, " as does bis(dicyclopropylmethylene)diazane, which gives an E/Z mixture of (dicyclopropyl)methyldiazene in 45% yield on treatment with lithium aluminum hydride. ... 

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