Threee-step synthesis of arylpolyboronic acids from phenols via organotin compounds

P.M. FIDELIBUS; G.F. SILBESTRI; M.T. LOCKHART; S.D.MANDOLESI; A.B. CHOPA; J.C. PODESTÁ

APPLIED ORGANOMETALLIC CHEMISTRY

Wiley- VCH

Lugar: Amsterdam; Año: 2007 p. 682 - 687

0268-2605

In this paper we describe a three-step synthesis of aryldi- and triboronic acids starting from phenols. Several substituted phenols (I) were converted into the corresponding aryldiethylphosphates (II) in good to excellent yields. The latter, on reaction with sodium trimethylstannide in liquid ammonia, under irradiation, afforded the aryl- and heteroarylpoly(trimethylstannyl) derivatives in 65–90% yield. The third step is the reaction of the organotin compounds with borane in THF, which leads to the corresponding arylpolyboronic acids in around 80% yield. In order to confirm their structure, some of the diboronic acids were converted into the corresponding pinacol esters. The results obtained in a study on the synthesis of various terphenyls through double and triple Suzuki couplings catalyzed by palladium acetate between the obtained arylpolyboronic acids and various aryl halides are also reported. These reactions proceeded with an average 65% yield, and also enabled us to confirm the structures of some of the diboronic acids. The structure of the new compounds was determined by 1H, 13C and 119Sn NMR spectroscopy, mass spectrometry and IR spectroscopy.H, 13C and 119Sn NMR spectroscopy, mass spectrometry and IR spectroscopy.