Trimethylstannyl amines, with

The five-membered heterocyclic ketone (39) has been prepared by the reaction of dimeric 5,5-dimethyl-l,3A, 2,4,5-dithiadiazastannole (40), obtained by the reaction of S4N4 with tris(trimethylstannyl)amine, with an excess of carbonyl difluoride at room temperature. The cyclic, ketone is the first representative of a new class of compounds that have become readily accessible by this method. 

New examples of the preparation of stannylamines, largely by established methods, are shown in Equations (164) and (165). Sodium bis(trimethylstannyl)amine can be prepared from sodium amide and a stannylamine,499 and can act as the precursor to other bis- and tris(stannyl)amino compounds.499 500 The tristannylamines are planar about the nitrogen, with the unshared pair in a 2p orbital. Tris(chlorodimethylstannyl)amine, with five-coordinate tin, is close to centrosymmetrical, and reacts with pyridine to give a tetrastannabicyclo[3.1.1]heptane.501... 

Tris(trimethylstannyl)amine reacts readily with fluorophosphazenes with cleavage of the Sn—N bond 119 e.g. 

Compound 86 highlights a more unusual 1,3,2,4-dithiadiazole <1975AGE498, 2004CPL516, 2005CPL440>. This five-membered heterocyclic ketone, which can be alternatively formulated as a meso-ionic l,3,2,4-dithiadiazolium-5-olate, is synthesized from tetrasulfur tetranitride and tris(trimethylstannyl)amine to form 5,5-dimethyl-l,3A4,2,4,5-dithiadiazastannole 87, which upon treatment with COF2 is converted into compound 86 in 49% yield, with dimethyltin fluoride as the by-product. 

Several examples of the use of hexamethyldistannoxane as a Me3Sn group transfer agent are reported. Thus the dimetallic carbonyl dimers of Mo, Mn, Fe, Co, and Ni react with Me3SnOSnMe3 [and also with tris(trimethylstannyl)amine, N(SnMe3)3] to form metal-carbonyl derivatives containing tin complexes (equation 118)277. 

Figure 11 Contour plot (adapted with permission from Ref. [38]) of the 2D 30.4 MHz N/ H HETCOR of tris(trimethylstannyl)amine, e3Sn>3N (25 °C 50% in C D basic 2D INEPT-based heteronuclear shift correlation). The drawn line in the formula shows the path of polarization transfer and the broken line connects those spins for which the sign of reduced coupling constants are compared. Four crosspeaks are visible corresponding to satellites. The positive tilt of those satellites corresponding to...

In a similar manner, the reaction of cyanuric fluoride 55 with tris(trimethylstannyl) amine in dry ether at 0 °C leads to the formation of 2,4-difluoro-6-[di(trimethylstannyl)]-amino-l,3,5-triazine 131 (Scheme 52) [5],... 

Scheme 52 Reaction of cyanuric fluoride 55 with tris(trimethylstannyl)amine...

Abel and Dunster have reported that dimethyl(trimethylstannyl)amine, on treatment with phenyl isothiocyanate, yields the trimethylstannyl-thiourea (301). On the other hand, Matsuda and his co-workers found that the related reaction of N-trimethylsilyl(diphenylmethylene)amines with isothiocyanates affords equilibrium mixtures of the two rapidly interconvertible tautomeric compounds (302) and (303). ... 

IV-Silyl Imines. When aldehydes were treated first with tris(trimethylstannyl)amine followed by TBDMSCl, the corresponding V-TBDMS imines were isolated in good yields. These silyl imines reacted with ester enolates to give p-lactams (eq 24). 

Diazo(trialkylsilyl)acetates 1 can be prepared conveniently from an alkyl diazoacetate and a trialkylsilyltriflate in the presence of a tertiary amine (path A). Furthermore, metalation of ethyl diazoacetate with butyllithium at — 110 °C, followed by addition of chlorotrimethylsilane provides ethyl diazo(trimethylsilyl)acetate. Ethyl diazo(trimethylsilyl)acetate and the corresponding trimethylgermyl- and trimethylstannyl- substituted diazoacetate have been prepared from mercury bis(ethyl diazoacetate) and bis(trimethylsilyl-, germyl- or stannyl)sulfide (path B). Ethyl diazo(trimethylgermyl)- and ethyl diazo(trimethylstannyl)acetate were obtained from ethyl diazoacetate and diethylaminotrimethyltin or -germanium (path C). Similarly, the ethyl (trimethylplumbyl)diazoacetate was obtained from bis(trimethylsilyl)aminotrimethyl-lead. 2... 

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