20068-04-6Relevant articles and documents
Direct Synthesis of α,β-Unsaturated Nitriles Catalyzed by Nonionic Superbases
D'Sa, Bosco A.,Kisanga, Philip,Verkade, John G.
, p. 3961 - 3967 (1998)
We report herein the use of 3-30 mol % of a new class of tricyclic strong nonionic Lewis bases P(MeNCH2CH2)3N and P(HNCH2CH2)(i-PrNCH2CH2) 2N for the direct catalytic synthesis of a variety of functionalized α,β-unsaturated nitriles in high yields from aldehydes and acetonitrile or benzyl cyanide at 40-50°C. Evidence for a novel mechanistic pathway proposed for this reaction in a polar protic solvent such as methanol, and a nonpolar aprotic solvent such as benzene is also presented. Under these conditions, primary and secondary aliphatic aldehydes do not condense satisfactorily with acetonitrile to give the α,β-unsaturated nitrile, and ketones do not condense with either benzyl cyanide or acetonitrile.
Allyl-Nickel Catalysis Enables Carbonyl Dehydrogenation and Oxidative Cycloalkenylation of Ketones
Huang, David,Szewczyk, Suzanne M.,Zhang, Pengpeng,Newhouse, Timothy R.
supporting information, p. 5669 - 5674 (2019/04/26)
We herein disclose the first report of a first-row transition metal-catalyzed α,β-dehydrogenation of carbonyl compounds using allyl-nickel catalysis. This development overcomes several limitations of previously reported allyl-palladium-catalyzed oxidation, and is further leveraged for the development of an oxidative cycloalkenylation reaction that provides access to bicycloalkenones with fused, bridged, and spirocyclic ring systems using unactivated ketone and alkene precursors.
A NOVEL SYNTHESIS OF α,β-UNSATURATED NITRILES FROM AROMATIC KETONES VIA CYANOPHOSPHATES
Harusawa, Shinya,Yoneda, Ryuji,Kurihara, Takushi,Hamada, Yasumasa,Shioiri, Takayuki
, p. 427 - 428 (2007/10/02)
Reaction of aromatic ketones with diethyl phosphorocyanidate in the presence of lithium cyanide gave cyanophosphates, which were converted into α,β-unsaturated nitriles by treatment with boron trifluoride etherate in high yields.
