SYNTHESIS OF METAL- AND PENTEL-CONTAINING HETEROCYCLES USING NITRILES AND ISONITRILES

The reaction of benzylnitrile with InMe 3 in a molar ratio of 3:1 leads to 2-amino-N-[Me 2 In(TMEDA)]-4-amino-3,5-diphenyl-6-benzyl-pyridine 2. CsF accelerates the reaction. The treatment of Ph 2 CHCN with InMe 3 in the presence of CsF gives the metalated ketenimine [(THF)Me 2 InNCCPh 2 ] 2 3. 3 and the corresponding Ga compound also can be obtained by the metathesis reaction of Me 2 MCl with LiNu═C═CPh 2 . The attack of the Lewis bases t BuELi 2 (E = P, As) on nitriles and isonitriles also leads to oligomerizations. t BuAsLi 2 reacts with two molecules of PhCN to the aromatic heterocycle [AsNC(Ph)NC(Ph)]− by forming the salt [Li(diglyme) 2 ] [(TMEDA)Li([AsNC(Ph)NC(Ph)]) 2 ] 4, while the reaction of t BuAsLi 2 with three equivalents of c HexNC leads to the dilithium compound [{Li 2 (diglyme)} 2 { t BuAs(CN c Hex) 3 } 2 ] 5. Six molecules c HexNC were consumed when Li 2 P t Bu was added to the isonitrile to give [{Li(DME)} 2 { t BuP(CN c Hex) 5 (CH)}] 6.