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Reactions of Furylruthenium Complexes with Oxygen and Trimethylsilyl Azide
Author(s) -
Chang KuHsien,
Sung HuiLing,
Lin YingChih
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200500621
Subject(s) - chemistry , ruthenium , azide , ring (chemistry) , medicinal chemistry , trimethylsilyl , trimethylsilyl azide , hydrolysis , bond cleavage , cleavage (geology) , stereochemistry , catalysis , organic chemistry , fracture (geology) , engineering , geotechnical engineering
The reaction of the (α‐alkoxyfuryl)ruthenium complexes 4 with oxygen opens the five‐membered furyl ring to give the addition product [Ru]O 2 CCR=CHCO 2 CH 3 , ( 5 , [Ru] = Cp(PPh 3 ) 2 Ru). Further reactions of 5 with CH 3 I and with organic acid gave CH 3 O 2 CCR=CHCO 2 CH 3 , ( 6 ), and HO 2 CCR=CHCO 2 CH 3 , ( 7 ), respectively. The reaction of 4 with TMSN 3 [TMS = (CH 3 ) 3 Si] gives the ruthenium azide [Ru]–N 3 and α‐alkoxyfuran, which is readily hydrolyzed to lactone in acidic medium. Treatment of the cyclopropenylruthenium complex 11b containing a methyl crotonate group with TMSN 3 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 TMSN 3 to olefinic carbon atoms of intermediates formed during the reaction.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)