Journal of Organic Chemistry p. 4510 - 4520 (1995)
Update date:2022-08-03
Topics:
Frimer, Aryeh A.
Marks, Vered
Gilinsky-Sharon, Pessia
Aljadeff, Gladis
Gottlieb, Hugo E.
Three reductones, 2,3-dihydroxy-4,4-diphenyl-2,5-cyclohexadien-1-one (11), 3,4-dihydroxycoumarin (35), and 3,4-dihydroxyspiro<5.5>undecan-3-en-4-one (64), were prepared and subsequently reacted with superoxide anion radical (O2(.-), generated from KO2 and 18-crown-6-polyether.The reactions were carried out in aprotic media and quenched with methyl iodide which facilitates the trapping of the various oxyanions formed.While a plethora of products were formed in each case <2-hydroxy-2-methyl-4,4-diphenyl-5-cyclohexene-1,3-dione (17), dimethyl 4,4-diphenylglutaconate (18), methyl 4,4-diphenyl-3-butenoate (19), phenylcinnamaldehyde (20), methyl 3-phenylcinnamate (21), and benzophenone (22) from 11; 3-hydroxy-2-methoxycoumarin (39), 2-carbomethoxy-2-hydroxy-3=coumaranone (40), 2-hydroxy-2-methyl-3-coumaranonr (41), methyl o-hydroxyphenylglyoxylate (42), methyl salicylate (43), and catechol (44) from 35; and 2,4-dihydroxyspiro<5.5>undeca-1,4-dien-3-one (66), 2-hydroxyspiro<4.5>dec-1-en-3-one (70), dimethyl 1,1-cyclohexanediacetate (73), and dimethyl α-keto-1-<(methoxycarbonyl)methyl>cyclohexane-1-propionate) (75) from 64> an overall analysis of the product distribution indicates that the basic elements of the reaction sequence are the same.The first step involves facile deprotonation and the concomitant generation of the reductone monoanion, a process which lends support to the suggestion of Afanas'ev and co-workers (Afanas'ev, I.B., Grabovietskii, V.V.; Kuprianova, N.S. J.Chem.Soc.Perkin Trans. 2 1987, 281-285).Oxidation of this monoanion yields the corresponding triketone.Of the various options available to this polyketone, superoxide attack at the most electrophilic central carbonyl followed by oxidative cleavage and/or benzylic acid rearrangement are clearly the most prominent.These are followed by a variety of base catalyzed autoxidative processes which are highly dependent on the nature of the substrate.
View MoreContact:+86-10-59484199
Address:No.58-A1026 Liangguan Street
Hangzhou Pharma & Chem Co.,Ltd.
Contact:+86-571-87040515
Address:No,139Qingchun Rd
Zhejiang Golden-Shell Pharmaceutical Co.,Ltd.
Contact:+86-576-87501888 / 87501988
Address:No.89 Zhongxing Road. Li'ao, Yuhuan, Zhejiang, China
Contact:+86-22-26358246
Address:601-4-20, Fujiayuan, Tiantai Road, Hebei District, Tianjin, China
wuhan new zhike bio chemical company
Contact:15827556622
Address:Hubei Wuhan
Doi:10.1021/ja01060a032
(1964)Doi:10.1016/0040-4020(78)80118-5
(1978)Doi:10.1021/ja045557j
(2004)Doi:10.1021/om100803g
(2010)Doi:10.1021/ja00795a026
(1973)Doi:10.1016/j.tetlet.2018.07.012
(2018)