Tributylstannyl ethers regioselectivity

Simple 2,2-dibutyl-l,3,2-dioxastannolanes form solid complexes of monomer units with certain nucleophiles, such as pyridine and dimethyl sulfoxide, that have 1 1 stoichiometry and pentacoordinate tin atoms.62 Such complexes are less stable for more-substituted stannylene acetals, such as those derived from carbohydrates.62 Unfortunately, the precise structures of these complexes have not yet been defined. Addition of nucleophiles to solutions of stannylene acetals in nonpolar solvents has been found to markedly increase the rates of reaction with electrophiles,63 and transient complexes of this type are likely intermediates. Similar rate enhancements were observed in reactions of tributylstannyl ethers.57 Tetrabu-tylammonium iodide was the nucleophile used first,57 but a wide variety of nucleophiles has been used subsequently tetraalkylammonium halides, jV-methylimidazole,18 and cesium fluoride64,65 have been used the most. Such nucleophilic solvents as N,N-dimethylformamide and ethers probably also act as added nucleophiles. As well as increasing the rates of reaction, in certain cases the added nucleophiles reverse the regioselectivity from that observed in nonpolar solvents.18,19... 

VII. Factors That Influence Reaction Regioselectivity 1. Tributylstannyl Ethers... 

Although the factors that influence the regioselectivities obtained from dialkylstannylene acetals are considerably more complicated than with tributylstannyl ethers, the outcome in most cases is surprisingly similar. The factor influencing regioselectivity in the absence of added nucleophiles will be discussed first. 

Fig. 24.—Regioselectivity in the benzoylation of the tributylstannyl ether of methyl a-o-glucopyranoside.74...

Fig. 26.—Regioselective alkylation of a tributylstannyl ether of a mannopyranose derivative.122...

Alkyl stannyl selenides are also useful nucleophilic selenium reagents. Tri-methylstannyl or tributylstannyl methyl selenides 58 react with halides 59 to produce unsymmetrical selenides 60 in good yields in the presence of a fluoride ion or by treatment with n-butyllithium (Scheme 44) [84]. Tributylstannyl phenyl selenide (61) reacts smoothly with acetals to give monoselenoacetals 62 in the presence of boron trifluoride etherate (Scheme 45 a) [85]. Similar reaction conditions were applied to the regioselective ring opening of epoxides (Scheme 45b) [86]. 

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