Synthesis of heteronuclear bifunctional Lewis acids by transmetalation of 1,8-bis(trimethylstannyl)naphthalene with BCl3

Abstract

Reaction of 1,8-bis(trimethylstannyl)naphthalene (1) with an excess of BCl3 at –78°, followed by warming to 0°C, results in the exclusive formation of the novel bifunctional Lewis acid 1-(chlorodimethylstannyl)-8-(dichloroboryl)naphthalene (2), a compound in which a boryl and a stannyl moiety coexist at the peri-positions of a naphthalene core. At elevated temperature compound 2 undergoes a chloride–methyl exchange, which affords 1-(dichloromethylstannyl)-8-(chloromethylboryl)naphthalene (3). Compounds 2 and 3 have been characterized by multi-nuclear NMR spectroscopy. The single crystal X-ray analysis for compound 3 reveals a sterically crowded structure with an essentially trigonal planar boron center, and a tin center pentacoordinated in a [4+1]-fashion. Upon exposure to traces of water, compound 3 is converted into the borinic acid derivative 1-(dichloromethylstannyl)-8-(hydroxymethylboryl)naphthalene (4), which has been characterized by multi-nuclear NMR spectroscopy and single crystal X-ray analysis.Key words: multidentate Lewis acids, organoboranes, organostannanes.