Methyl trimethylstannyl

Aus Thiophosphorylchlorid und Heptamethyldistannazan ist Thiophosphorsdure-dichlo-rid-(methyl-trimethylstannyl-amid) (92% Schmp. 26—28°)48 zuganglich ... 

Dichlorphosphoryl-(dichlor-thiophosphoryl)-mcthyl-amin entsteht auch durch Kochen von Thiophosphorsaure-dichlorid-(methyl-trimethylsilyl-amid) mit iiberschiissigem Phosphorylchlorid (Ausbeute 42%)47. Analog reagiert Thiophosphorsaure-difluorid-(methyl-trimethylstannyl-amid) mit Pyrophosphorylfluorid zu Difluorphosphoryl-(di-fluor-thiophosphoryl)-methyl-amin (88% Sdp 47°/20 Torr/2,7 kPa)50 ... 

Trimethylstannyl chloride reacted smoothly with methyl and phenyl trimethylsilyl tellurium at 25°. Methyl trimethylstannyl tellurium (94% yield) and phenyl trimethylstannyl tellurium (89% yield) were isolated as involatile, yellow oils possessing foul, persistent odors1. 

Methyl trimethylstannyl tellurium was obtained when trimethylstannane reacted with methyl bis[trifluoromethyl]phosphano or -arsano tellurium2,3.The products were not isolated but identified by NMR spectroscopy. 

Oxidative addition of tetramethyltin to Pt(cod)2 and exchange of the ligands produces methyl(trimethylstannyl)platinum(ii) complexes with cod and phosphine ligands 10 and 11 (Scheme 2). ... 

V-Methyl-7V-(trimethylplumbyl)gcrmanamine, see Pb-00069 Methyl trimethylplumbyl selenide, see Pb-00033 Methyl trimethylplumbyl telluride, see Pb-00034 Methyl trimethylstannyl selenide, see Sn-00079 Methyl trimethylstannyl sulflde, see Sn-00075 l-Methyl-2,8,9-trioxa-5-aza-l-stannabicyclo[3.3.3]undecanc, Sn-00139... 

Z,3R)- and (l ,35)- l-Methyl-3-(trimethylstannyl)-t-butenyl Diisopropylcarbamates via Lithiation Topical Procedure131 ... 

Methyl- C]thymine ([ C]FMAU) could be obtained in modest radiochemical yields via cross-coupling of [ CJmethyl iodide with l-(2 -deoxy-2 -fluoro-/3-D-arabinofuranosyl)-5-(trimethylstannyl)uracil. Optimal power was found to be 70W, since an increase to 100 W as well as a decrease to SOW resulted in lower radiochemical yields (Scheme 6). 

The foregoing stabilizing 1,3-diaxial interaction was shown to have potentially useful applications for stereochemical control of addition reactions56. The /l-trimethylstannyl cyclohexenone ketal 65 affords a nearly 1 1 mixture of isomeric c/s-diols 66 and 67 when hydroxylated with OsC>4 (equation 25). However, the chlorostannane 68 upon hydroxylation with OSO4, then Sn methylation, yields a 94 6 mixture favoring the a,a,-diol 66. Evidently, the conformational change induced by the 1,3-diaxial donor-acceptor... 

The two trimethylstannyl groups are crystal- 210 lographically equivalent, however, the three methyl groups are rotationally and vibrationally different, as shown by INS spectroscopy at low temperature. 

Dipolar cycloaddition reaction of trimethylstannylacetylene with nitrile oxides yielded 3-substituted 5-(trimethylstannyl)isoxazoles 221. Similar reactions of (trimethylstannyl)phenylacetylene, l-(trimethylstannyl)-l-hexyne, and bis (trimethylsilyl)acetylene give the corresponding 3,5-disubstituted 4-(trimethyl-stannyl)isoxazoles 222, almost regioselectively (379). The 1,3-dipolar cycloaddition reaction of bis(tributylstannyl)acetylene with acetonitrile oxide, followed by treatment with aqueous ammonia in ethanol in a sealed tube, gives 3-methyl-4-(tributylstannyl)isoxazole 223. The palladium catalyzed cross coupling reaction of... 

Bailey described the first application of the Stille coupling to pyrroles, and one of the earliest examples of any such reaction involving heterocycles [66]. Lithiation of IV-methylpyrrole and quenching with trimethylstannyl chloride gives 2-(trimethylstannyl)pyrrole (76), and palladium-catalyzed coupling with iodobenzene affords l-methyl-2-phenylpyrrole (46) in good yield. 

We note that while tin reagents have often been employed for the organoboron halides/ the use of organostannanes as starting materials can also be applied to the synthesis of heavier group 13 derivatives. In the context of polyfunc-tional Lewis acid chemistry, this type of reaction has been employed for the preparation of ort/ o-phenylene aluminum derivatives. Thus, the reaction of 1,2-bis(trimethylstannyl)benzene 7 with dimethylaluminum chloride, methylaluminum dichloride or aluminum trichloride affords l,2-bis(dimethylaluminum)phenylene 37, l,2-bis(chloro(methyl)aluminum)phenylene 38 and 1,2-bis(dichloroalumi-num)phenylene 39, respectively (Scheme 16). Unfortunately, these compounds could not be crystallized and their identities have been inferred from NMR data only. In the case of 39, the aluminum derivative could not be separated from trimethyltin chloride with which it reportedly forms a polymeric ion pair consisting of trimethylstannyl cations and bis(trichloroaluminate) anions 40. 

TMEDA can be deprotonated on a methyl gronp, bnt the only reaction reported was with the electrophile trimethylstannyl chloride. ... 

In analoger Weise, jedoch mit anderer Regioselektivitat, fuhrt die Reaktion von 2-Methyl-oxiran mit Diethylamino-trimethyl-stannan bzw. Piperidino-trimethyl-stannan zu den S-Trimethylstannyl-Derivaten der entsprechenden l-Dialkylamino-2-mercapto-propane, die mittels Malonsaure unter Bildung von l-Diethylamino-2-mercapto-propan (71%) bzw. 2-Mercapto-l-piperidino-propan (68%) gespalten werden konnen2 ... 

Lithium metal or alkyllithium derivatives react with dihalocyclopropanes to provide the corresponding lithiohalocyclopropanes I which are stable at temperatures around —100 °C. These metalated species are easily trapped with electrophiles (R—X) like methyl or ethyl iodide, trimethylstannyl chloride, tri-methylsilyl chloride etc. In the case of the unsaturated bicyclic substrate II a double bond migration is observed, which in the presence of excess starting bromide is accompanied by isomerization of the axo-lithio intermediate III to its endo-isomer IV [58],... 

Treatment of the coordinatively unsaturated osmium trimethylstannyl complex Os(SnMe3)Cl(CO)(PPh3)2 with sodium acetate results in methyl group migration from tin to osmium with formation of the Os-Sn-O-C-O heterocycle 150, which has been characterized by NMR, IR, and X-ray crystallography (Equation 16) <1999CC1101>. 

Other trialkyltin-containing monomers such as 3-tributyltinstyrene (84), tributyltin methacrylate (85) and 4-[bis(trimethylstannyl)methyl]styrene (86) were also reported to homo- and copolymerise with styrene under radical conditions175-177. In addition, 3-tributyltinstyrene (84) was copolymerised under radical conditions with ethyl acrylate, methyl methacrylate, vinyl acetate and acrylonitrile175. A functional methacrylate-based polymer was prepared by the copolymerization of the triorganotin methacrylate monomer 87 with styrene and divinylbenzene178,179. 

SCHEME 49. Preparation of SnC>2 via poly 4-[(trimethylstannyl)methyl]styrene (96)... 

A requirement for an a/m-orientation of the hydridic p-C—H and C—metal bonds as in [10] is indicated by the reaction of threo-3-deuterio-2-(trimethylstannyl)butane with triphenylcarbenium tetrafluoroborate in methylene chloride at 24° which yields a mixture of 3-deuterio-l -butene, /ra v-2-deuterio-2-butene, and undeuteriated c/.v-2-butene as the major product (Hannon and Traylor, 1981). Comparison of the product distributions for the protio- and deuterio-stannanes yields primary and secondary isotope effects of 3.7 and 1.1 respectively. These reactions appear to avoid the complications of adduct formation between the triarylcarbenium salt and the hydride donor, but the preferential formation of the cw-2-butenes is not fully explained. The requirement for the anti-orientation is also shown by the relatively low hydride-donating properties of tris[(triphenylstannyl)methyl-methane (Ducharme et ai, 1984a) which adopts a C3-conformation with the P-C—H gauche to all three C—Sn bonds. In contrast, 1,3,5-triphenyl-2,4,6-trithia-1,3,5-tristannyladamantane, in which anti-orientations with respect to the bridgehead C—H bond are locked, shows high reactivity (Ducharme et al., 1984b). 

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