Protonated Aminocyclopentadienyl Ruthenium Hydride Reduction of Benzaldehyde and the Conversion of the Resulting Ruthenium Triflate to a Ruthenium Hydride with H2 and Base
摘要:
Reaction of N-phenyl-2,5-dimethyl-3,4-diphenylcyclopenta-2,4-dienimine (6) with Ru3CO12 formed two isomers of {[2,5-Me-2-3,4-Ph-2(eta(5) -C4CNHPh)]Ru(CO)(mu-CO)}(2) (8-trans and 8-cis). Photolysis of 8 under a H-2 atmosphere led to the formation of the aminocyclopentadienyl ruthenium hydride [2,5-Me-2-3,4-Ph-2(eta(5)-C4CNHPh)]Ru(CO)(2)H (9-H). 9-H reduced benzaldehyde slowly at 75 degreesC to give benzyl alcohol and 8. Protonation of 9-H with triflic acid produced {[2,5-Me-2-3,4-Ph-2(eta(5)-C4CNH2Ph)]Ru(CO)(2)H}OTf (11-H), which reacted rapidly with benzaldehyde at -80 degreesC to give benzyl alcohol and [2,5-Me-2-3,4-Ph-2(eta5-C4CNHPh)]Ru(CO)(2)OTf(9-OTf). Reaction of 9-OTf with H2 and base led to the re-formation of 9-H. These reactions provide the transformations required for a catalytic cycle for hydrogenation of aldehydes.
Protonated Aminocyclopentadienyl Ruthenium Hydride Reduction of Benzaldehyde and the Conversion of the Resulting Ruthenium Triflate to a Ruthenium Hydride with H2 and Base
摘要:
Reaction of N-phenyl-2,5-dimethyl-3,4-diphenylcyclopenta-2,4-dienimine (6) with Ru3CO12 formed two isomers of {[2,5-Me-2-3,4-Ph-2(eta(5) -C4CNHPh)]Ru(CO)(mu-CO)}(2) (8-trans and 8-cis). Photolysis of 8 under a H-2 atmosphere led to the formation of the aminocyclopentadienyl ruthenium hydride [2,5-Me-2-3,4-Ph-2(eta(5)-C4CNHPh)]Ru(CO)(2)H (9-H). 9-H reduced benzaldehyde slowly at 75 degreesC to give benzyl alcohol and 8. Protonation of 9-H with triflic acid produced {[2,5-Me-2-3,4-Ph-2(eta(5)-C4CNH2Ph)]Ru(CO)(2)H}OTf (11-H), which reacted rapidly with benzaldehyde at -80 degreesC to give benzyl alcohol and [2,5-Me-2-3,4-Ph-2(eta5-C4CNHPh)]Ru(CO)(2)OTf(9-OTf). Reaction of 9-OTf with H2 and base led to the re-formation of 9-H. These reactions provide the transformations required for a catalytic cycle for hydrogenation of aldehydes.
Exploiting the Nucleophilicity of NH Imines: Synthesis of Enamides from Alkyl Azides and Acid Anhydrides
作者:Junghoon Han、Mina Jeon、Han Kyu Pak、Young Ho Rhee、Jaiwook Park
DOI:10.1002/adsc.201400584
日期:2014.9.15
The nucleophilicity of N‐unsubstituted imines, which were generated from alkyl azides by a ruthenium‐catalyzedreaction, was investigated in the reaction with acid anhydrides. The initial products were N‐acylimines, which isomerized to the corresponding enamides. Heating or triethylamine facilitated the isomerization of N‐acylimines that are stable at room temperature. A wide range of acyclic and cyclic