Organotin reactions with

Alkyltin Intermedia.tes, For the most part, organotin stabilizers are produced commercially from the respective alkyl tin chloride intermediates. There are several processes used to manufacture these intermediates. The desired ratio of monoalkyl tin trichloride to dialkyltin dichloride is generally achieved by a redistribution reaction involving a second-step reaction with stannic chloride (tin(IV) chloride). By far, the most easily synthesized alkyltin chloride intermediates are the methyltin chlorides because methyl chloride reacts directiy with tin metal in the presence of a catalyst to form dimethyl tin dichloride cleanly in high yields (21). Coaddition of stannic chloride to the reactor leads directiy to almost any desired mixture of mono- and dimethyl tin chloride intermediates ... 

The reaction is of practical importance in the vulcanization of siUcone mbbers (see Rubber compounding). Linear hydroxy-terrninated polydimethyl siloxanes are conveniently cross-linked by reaction with methyldiethoxysilane or triethoxysilane [998-30-1]. Catalysts are amines, carboxyflc acid salts of divalent metals such as Zn, Sn, Pb, Fe, Ba, and Ca, and organotin compounds. Hydroxy-terrninated polysiloxanes react with Si—H-containing polysiloxanes to... 

Intramolecular Pd(0)-catalyzed Stille reaction of organotin reagents with electrophiles leading to C—C a-bond formation in synthesis of heterocycles, particularly, macrocyclic lactones 99JCS(P1)1235. 

Besides a polymerization of the Michael acceptor, a double alkylation of the starting ketone, by reaction with a second Michael acceptor molecule, may take place as a side reaction, and thus further reduce the yield. The polymerization of the enone 2 as well as the double alkylation of the starting ketone can be avoided by application of a modern procedure for the Robinson annulation that uses an organotin triflate as catalyst." ... 

Coupling reaction of organotin compounds with carbon electrophiles... 

By reaction with the appropropriate aryl halides can be prepared a variety of aryltin compounds that are not accessible from the reactions involving arylmagnesium halides and organotin halides (88,89) there is evidence that an aryne intermediate may be involved (90). However, for some purposes, such as the addition to carbonyl compounds, ox-iranes, and oxetanes, to give hydroxyalkyltin compounds, the Sn-Mg reagents may have advantages (see Section II,E) (91-93). 

A lot of attention has also been paid to the reaction of organotin compounds with sulfur dioxide to give organotin sulfinates (116-119). 

Organotin Hydrides, Reactions with Organic Compounds, 1, 47... 

The MH-type reaction of silanols and organotin compounds with olefins via a Pd(II)-mediated pathway has been reported by Hiyama and co-workers. Based on this pathway, a plausible MH-type reaction mechanism with arylboronic acids was presented in Fig. 26. According to this mechanism, the aryl unit migrated to... 

Reactions of Allylic Trialkylstannnanes. Allylic organotin compounds are not sufficiently reactive to add directly to aldehydes or ketones, although reactions with aldehydes do occur with heating. 

In basic aqueous media, a kinetic study of the reaction between stannate(II) ions and alkyl halide shows that mono- and disubstituted organotin compounds are formed (Eq. 6.12a).27 The monosubstituted organotin compound is obtained after a nucleophilic substitution catalyzed by a complexation between the tin(II) and the halide atom. The disubstituted compound results from an electrophilic substitution coupled with a redox reaction on a complex between the monosubstituted organotin compound and the stannate(II) ion. Stannate(IV) ions prevent the synthesis of the disubstituted compound by complexation. Similarly, when allyl bromide and tin were stirred in D2O at 60° C, allyltin(II) bromide was formed first. This was followed by further reaction with another molecule of allyl bromide to give diallyltin(IV) dibromide (Eq. 6.12b).28... 

However, cycloauration is, sometimes, difficult to achieve with direct activation of a C—H bond and transmetallation reaction of organomercury or organotin compounds with the appropriate gold compounds is, hence, frequently used. This procedure has been used with azobenzene, 36 A, A -dimethylbenzilamine,1937,1938 4,4 -dimethyl-2-phenyl-l, 3-oxaazoline,1938 1 - (dii zene,... 

Pentadienyltrimethylstannanes undergo regioselective conjugate additions to aldehydes, catalysed by Lewis acids. The dominant product obtained depends on the catalyst used, as shown in reaction 46. In the case of titanium tetrachloride catalysis the reaction is also stereoselective and only one diasteroisomer is obtained297. Reaction with chiral aldehydes leads to asymmetric induction with similar organotin compounds298. 

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