Reactions of furylruthenium complexes with oxygen and trimethylsilyl azide

摘要

The reaction of the (alpha-alkoxyfuryl)ruthenium complexes 4 with oxygen opens the five-membered furyl ring to give the addition product [Ru]O2CCR=CHCO2CH3, (5, [Ru] = Cp(PPh3)(2)Ru). Further reactions of 5 with CH3I and with organic acid gave CH3O2CCR=CHCO2CH3, (6), and HO2CCR=CHCO2CH3, (7), respectively. The reaction of 4 with TMSN3 [TMS = (CH3)(3)Si] gives the ruthenium azide [Ru]-N-3 and alpha-alkoxyfuran, which is readily hydrolyzed to lactone in acidic medium. Treatment of the cyclopropenylru- thenium complex 11b containing a methyl crotonate group with TMSN3 affords the five-membered-ring triazole and [Ru]-CN. In this reaction cleavage of the C=C double bond of the three-membered ring could be caused by consecutive additions of TMSN3 to olefinic carbon atoms of intermediates formed during the reaction. (c) Wiley-VCH Verlag GmbH & Co. KGaA.