15174-78-4Relevant academic research and scientific papers
Palladium-Catalyzed Cascade Carbonylation to α,β-Unsaturated Piperidones via Selective Cleavage of Carbon–Carbon Triple Bonds
Beller, Matthias,Ge, Yao,Jackstell, Ralf,Jiao, Haijun,Spannenberg, Anke,Yang, Ji,Ye, Fei
supporting information, p. 22393 - 22400 (2021/09/08)
A direct and selective synthesis of α,β-unsaturated piperidones by a new palladium-catalyzed cascade carbonylation is described. In the presented protocol, easily available propargylic alcohols react with aliphatic amines to provide a broad variety of interesting heterocycles. Key to the success of this transformation is a remarkable catalytic cleavage of the present carbon–carbon triple bond by using a specific catalyst with 2-diphenylphosphinopyridine as ligand and appropriate reaction conditions. Mechanistic studies and control experiments revealed branched unsaturated acid 11 as crucial intermediate.
ALLYLIC REARRANGEMENT OF CYANOPHOSPHATE. II. SYNTHESIS OF β-CYANO-α,β-UNSATURATED KETONES
Kurihara, Takushi,Miki, Masuo,Yoneda, Ryuji,Harusawa, Shinya
, p. 2747 - 2753 (2007/10/02)
Boron trifluoride-catalyzed allylic rearrangement of the cyanophosphates of α,β-unsaturated ketones (1a-d, 7 and 14) was found to give the allylic phosphates (3a-d, 9 and 16), which were successfully converted to β-cyano-α,β-unsaturated ketones (6a-d, 13 and 20) by acid hydrolysis (0.5 N HCl) followed by manganese dioxide oxidation of the resulting allylic alcohols(5a-d, 11, 12 and 17).The stereochemical features of the allylic phosphates (9 and 16) are discussed.Keywords-α,β-unsaturated ketone; diethyl phosphorocyanidate; cyanophosphate; allylic rearrangement; boron trifluoride etherate; manganese dioxide; β-cyano-α,β-unsaturated ketone
Michael Reaction of Conjugated Nitro Olefins with Carboxylic Acid Dianions and with Ester Enolates: New Synthesis of γ-Keto Acids and γ-Keto Esters
Miyashita, Masaaki,Yamaguchi, Ryuji,Yoshikoshi, Akira
, p. 2857 - 2863 (2007/10/02)
Base-sensitive conjugated nitro olefins 2 reacted with lithium dianions of carboxylic acids 3 or with lithium enolates of esters 4 at a low temperature of ca. -100 deg C, and subsequent treatment of the Michael adducts with aqueous acid yielded γ-keto acids 5 or esters 5' in a one-pot operation, respectively.Results of both the reactions have been compared.Some applications of the resulting γ-keto esters in organic synthesis have also been demonstrated in lactone synthesis and cyclenone annulation.
