- Controllable chemoselectivity in the coupling of bromoalkynes with alcohols under visible-light irradiation without additives: Synthesis of propargyl alcohols and α-ketoesters
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The chemoselectivity of visible-light-induced coupling reactions of bromoalkynes with alcohols can be controlled by simple changes to the reaction atmosphere (N2 or O2). A N2 atmosphere favours propargyl alcohols via a direct C-C coupling process, whereas an O2 atmosphere results in the generation of α-ketoesters through the oxidative CC/C-O coupling pathway.
- Ni, Ke,Meng, Ling-Guo,Ruan, Hongjie,Wang, Lei
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supporting information
p. 8438 - 8441
(2019/07/22)
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- Syntheses of Aryl Glyoxylate. I. The Reaction of Alkyl Dichloro(alkoxy)acetates with Aromatics in the Presence of Lewis Acid
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Ethyl dichloro(ethoxy)acetate(1) and methyl dichloro(methoxy)acetate(2) were characterized.The reaction of 1 and 2 with aromatics in the presence of AlCl3 gave a considerable yield of aromatic α-keto ester.The aromatics included mono- and polymethylbenzene and anisol.The reaction was studied under various conditions and the results were compared with the acylation by ethoxalyl or methoxalyl chloride.The reaction mechanism was also discussed.
- Itoh, Osamu,Nagata, Takayoshi,Nomura, Isamu,Takanaga, Tetsuya,Sugita, Toshio,Ichikawa, Katsuhiko
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p. 810 - 814
(2007/10/02)
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- 1-Aryl-3-azabicyclohexanes, a New Series of Nonnarcotic Analgesic Agents
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A series of 1-aryl-3-azabicyclohexanes was synthesized by hydride reduction of 1-arylcyclopropanedicarboximides.Hydroxyphenyl analogues 20, 22, and 24 were prepared by EtSNa-DMF ether cleavage of the corresponding methoxyphenyl analogues 2m, 2n, and 23, respectively, with the secondary amines 20 and 22 going through the N-formyl intermediates 19 and 21.The p-ethoxy analogue 26 was obtained by O-ethylation of 19, followed by base hydrolysis of the amide 25.The greatest analgesic potency in mouse writhing and rat paw-pain assays was observed for para-substituted compounds.Bicifadine, 1-(4-methylphenyl)-3-azabicyclohexane (2b), was the most potent member of the series and is presently undergoing clinical trials in man.Analgesic activity of 2b is limited to the (+) enantiomer 2v, which has the 1R,5S absolute configuration as determined by single-crystal X-ray analysis.The N-methyl analogue (27d) of 2b showed significant analgesic potency, whereas the N-allyl (27a), N-(cyclopropylmethyl) (27b), and N-(n-hexyl) (27c) analogues were inactive.Bicifadine (2b) showed a nonnarcotic profile different from analogous azabicycloalkane and 3-phenylpyrrolidine analgesics.
- Epstein, Joseph W.,Brabander, Herbert J.,Fanshawe, William J.,Hofmann, Corris M.,McKenzie, Thomas C.,et al.
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p. 481 - 490
(2007/10/02)
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