Trimethylstannyl sodium

The reaction of trimethylstannyl sodium with primary halides has been studied in detail with emphasis on the effect of solvents and added radical and carbanion traps. By lowering... 

Yamamoto and Yanagi [24] have prepared iodoazines through iodo-destannation of trimethylstannylazines. Trimethylstannyl sodium was prepared in situ from chlorotrimethyl-stannane and metallic sodium. Subsequent treatment of 2-chloroquinoline 25 with trimethylstannyl sodium gave 2-trimethylstannylquinoline 41. Likewise, 3- and 4-trimethyl-stannyl quinolines 42 and 44 were converted to 3- and 4-iodoquinolines 43 and 45 in 96 and 91% yield, respectively via iodo-destannation. In the same fashion, 2,4-bis (trimethylstannyl)quinoline was synthesized from 4-bromo-2-chloroquinoline using two equivalents of trimethylstannyl sodium in 65% yield. 

The S Ar reaction between 2-chloroquinoline 25 and trimethylstannyl sodium led to 2-trimethylstannylquinoline 41 as shown previously. Similarly, 3-trimethylstannyl quinoline 49 and 4-trimethylstannyl quinoline 51 were prepared from 3-chloroquinoline 48 and... 

Trimethylstannyl)norbornene, see Sn-00206 Trimethylstannyl phenylsulfonate, see Sn-00180 (Trimethylstannyl)sodium, Sn-00039 -(Trimethylstannyl)succinimide, see Sn-00138 1 -(T rimethylstannyl)-1H-1,2,4-triazole, Sn-00089 Trimethylstannyltricarbonyl(i -cyclopcntadienyl)molybdcnum, see Sn-00216... 

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... 

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>. 

When /t-bis(trimethylstannyl)benzene was treated with sodium metal in liquid ammonia, a dianion was formed which upon photostimulation with CgHsCl afforded the disubstitution product in 70% yield (Scheme 35) . ... 

CYANHYDRINE d ACETONE (FRENCH) see MLC750 CYANIC ACID, POTASSIUM SALT see PLC250 CYANIC ACID, SODIUM SALT see COI250 CYANIC ACID, TRIMETHYLSTANNYL ESTER see TMIlOO... 

To a solution of the diene [51] (1 mmol) in anhydrous f-butanol (20 mL, 0.05 M) under argon, are added trimethyltin chloride (400 mg, 2 mmol), sodium cyanoborohydride (190 mg, 3 mmol), and AIBN (15 mg, 10%). The solution is refluxed for 1-20 h (until the diene disappears as monitored by TLC using KMnO spraying agent). The solution is cooled to room temperature, quenched with 5% ammonia solution, stirred, and concentrated under reduced pressure. The residue is dissolved in ether, washed three times with brine, dried (MgS04), and processed as usual. Flash chromatography afforded the trimethylstannyl derivative in 52% yield [a] -20° (c 0.6, CHCl,). 

Cleavage of the Sn—C bond in bis(trimethylstannyl)methane occursusing Na in liq NH3 with the formation of trimethyltin sodium and CH4. 

Pyridines (and quinolines) bearing a trimethylstannyl (SnMes) substituent at the 2-, 3-, or 4-position undergo iododemetallation to give the corresponding iodo-derivatives upon treatment with iodine. The trimethylstannyl compounds are themselves prepared by the reaction of the corresponding chloro-or bromo-derivatives with trimethylstannylsodium. The selective 3-debro-mination of 3,5-dibromo-4-hydroxy-2-pyridone has been reported. The reaction of 3-chloro-4-cyanopyridine with methanolic sodium methoxide gives the imino-ether (24) whereas treatment with sodium methoxide in DMF... 

Very few arsenicals of this type are known. Maier 291) has found that triphenylsilyl lithium couples with dibromomethylarsine forming CH3 As[Si(C6H5)3]2. Dimethylaminotrimethyltin and diphenylarsine give a nearly quantitative yield of diphenyl(trimethylstannyl)arsine 292). Similar compounds are obtained from trialkyltin halides and the sodium derivative of diphenylarsine 178a). 

Lithium chloride (106 mg, 2.50 mmol) and sodium carbonate (Na2C03, 160 mg, 1.50 mmol) were flame dried carefully in a round-bottomed flask under vacuum and cooled under N2(g). NMP (4 mL) was added, the suspension degassed and sonicated for 1 h, after which time 2-bromo-3,4-dihydronaphthalen-l-yl trifluoromethanesulfonate (179 mg, 0.50 mmol) was added. The reaction vessel was evacuated and stirred for a further 0.2 h, back-filled with N2(g) and Pd(dba)2 (28.4 mg, 0.05 mmol) and TFP (23.2 mg, 0.10 mmol) were added. The reaction mixture became dark brown, then pale yellow soon after. 2-Allyl-3-(trimethylstannyl)cyclohex-2-enone (200 mg, 0.67 mmol) was added, the reaction mixture heated to 55 °C for 0.2 h whilst monitored by TLC, after this time Cu(I)TC... 

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