Sonochemical synthesis of bis(tri-n-butylstannyl) aromatic compounds via Barbier-like reactions

• Synthesis of new aryl- and heteroaryl bis(tri-n-butylstannylated) compounds.
• Sonochemical Barbier-like synthesis of bis(tri-n-butylstannylated) aromatic compounds mediated by Mg.
• Use of bis(tri-n-butyltin) oxide and tri-n-butyltin chloride electrophiles for the synthesis of aryl tri-n-butyltin compounds.

This paper reports a study of the synthesis of aryltri-n-butylstannanes via a sonochemical Barbier reaction of aryl- and heteroaryl bromides with bis(tri-n-butyltin) oxide (2) in THF. Our results demonstrate that, despite previous reports on contrary, the aryltributylstannanes can also be obtained under the same reaction conditions via sonicated reactions between aryl monobromides and tri-nbutyltin chloride (2). A comparative study of the reactions of electrophiles 2 and 3 with bromobenzene, 2-bromopyridin, o- and m-bromoanisole, m-bromotoluene, 9-bromophenthrene, and 9-bromoanthracene, indicates that the corresponding aryl- and heteroaryl-tri-n-butylstannyl derivatives are obtained in about the same yields. Best reaction conditions and the results obtained in the investigation of the sonicated reactions between several aromatic and heteroaromatic dibromides are also reported. It was found that the reactions using 1,2-, 1,3-, and 1,4-dibromobenzenes, 4,4′-dibromobiphenyl, 1,4-dibromonaphthalene, 2,5- and 3,5-dibromopyridines, and 2,5-dibromothiophene lead to the corresponding bis(tri-n-butylstannylated) derivatives in many cases in very high yields. Also the excellent results obtained in the sonicated reactions of 1,3,5-tribromobenzene with 2 and 3 are reported.

The best reaction conditions and the syntheses of some new bis(tri-n-butylstannylated) aromatic and heteroaromatic compounds by means of a Barbier-like sonochemical reaction are reported. Full 1H-, 13C-, and 119Sn NMR data of the new organotin compounds are informed.Figure optionsDownload as PowerPoint slide