Abstract
The total chemical synthesis of isoacteoside (1), 2-(3′,4′-dihydroxyphenyl)ethyl 6-O-caffeoyl-3-O-(α-l-rhamnopyranosyl)-β-d-glucopyranoside, is described. An acteoside acetate with benzyl groups at the catechols (3: 2-(3′,4′-dibenzyloxyphenyl)ethyl 2,6-di-O-acetyl-4-O-[3′,4′-bis(O-benzyl)caffeoyl]-3-O-(α-l-rhamnopyranosyl)-β-d-glucopyranoside) was treated with a solution of methy-lamine in methanol (MeNH2 in MeOH) to perform both deacetylation and caffeoyl migration, affording an isoacteoside derivative with benzyl groups at the catechols4b: 2-(3′,4′-dibenzyloxyphenyl)ethyl 6-O-[3′,4′-bis(O-benzyl) caffeoyl] -3-O-(α-l-rhamnopyranosyl)-β-d-glucopyranoside —in 34% yield. Debenzylation of4b was successfully accomplished by catalytic transfer hydrogenation using 1,4-cyclohexadiene to give the target compound isoacteoside (1) in 54% yield.1H and13C nuclear magnetic resonance spectral data of the synthesized isoacteoside (1) were identical with those of the natural isoacteoside isolated fromPaulownia tomentosa (Thumb.) Steud.
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Jiménez C, Riguera R (1994) Phenylethanoid glycosides in plants: structure and biological activity. Nat Prod Rep 11:591–606
Cometa F, Tomassini L, Nicoletti M (1993) Phenylpropanoid glycosides: distribution and pharmacological activity. Fitoterapia 64:195–217
Mølgaard P, Ravn H (1988) Evolutionary aspects of caffeoyl ester distribution in dicotyledons. Phytochemistry 27:2411–2421
Xiong Q, Hase K, Tezuka Y, Tani T, Namba T, Kodata S (1997) Hepatoprotective activity of phenylethanoids fromCistanche deserticola. Planta Med 64:120–125
Kawada T, Asano R, Hayashida S, Sakuno T (1999) Total synthesis of the phenylpropanoid glycoside, acteoside. J Org Chem 64:9268–9271
Kawada T, Asano R, Makino K, Sakuno T (2000) Synthesis of conandroside: a dihydroxyphenylethyl glycoside fromConandron ramaidioides. Eur J Org Chem 2000:2723–2727
Pettit GR, Numata A, Takemura T, Ode RH, Narula AS, Schmidt JM, Cragg GM, Pase CP (1990) Antineoplastic agents, 107: isolation of acteoside and isoacteoside fromCastilleja linariaefolia. J Nat Prod 53:456–458
Scarpati ML, Monache FD (1963) Isolamento dal verbascum sinuatum di due nuovi glucosidi: il verbascoside e l'isoverbascoside. Ann Chem 53:356–367
Miyase T, Koizumi A, Ueno A, Noro T, Kuroyanagi M, Fukushima S, Akiyama Y, Takemoto T (1982) Studies on the acyl glycosides formLeucosceptrum japonicum (Miq.) Kitamura et Murata. Chem Pharm Bull (Tokyo) 30:2732–2737
Schilling G, Hügel M, Mayer W (1982) Verbascoside und Isoverbascoside ausPaulownia tomentosa Steud. Z Naturforsch 37b:1633–1635
Sasaki H, Nishimura H, Morota T, Chin M (Chen Z), Mitsuhashi H, Komatsu Y, Maruyama H, Tu G, He W, Xiong Y (1989) Immunosuppressive principles ofRehmannia glutinosa var.hueichingensis. Planta Med 55:458–562
Ota M, Azuma T, Onodera S, Taneda K (1993) The chemistry of color changes in kiri wood (Paulownia tomentosa Steud.) III. A new caffeic acid sugar from kiri wood. Mokuzai Gakkaishi 39:479–485
Duynstee HI, de Koning MC, Ovaa H, van der Marel GA, van Boom JH (1999) Synthesis of verbascoside: a dehydroxyphenylethyl glycoside with diverse bioactivity. Eur J Org Chem 1999:2623–2632
Zhang SQ, Li ZJ, Wand AB, Cai MS, Feng R (1998) Synthesis of a phenylpropanoid glycoside, osmanthuside B6. Carbohydr Res 308:281–285
Ota M, Takahashi K, Kofujita H (1998) Role of caffeic glucoside esters in defense-repair processing of trees. II. Synthesis of 2-(3,4-dihydroxyphenyl)-ethyl 3-O-α-L-rhammopyranosyl-β-d-glucopyranoside. J Wood Sci 44:320–326
Felix AM, Heimer EP, Lambros TJ, Taougraki C, Meinenhofer J (1978) Rapid removal of protecting groups from peptides by catalytic transfer hydrogenation with 1,4-cyclohexadiene. J Org Chem 21:4194–4196
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Kawada, T., Asano, R., Makino, K. et al. Synthesis of isoacteoside, a dihydroxyphenylethyl glycoside. J Wood Sci 48, 512–515 (2002). https://doi.org/10.1007/BF00766648
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DOI: https://doi.org/10.1007/BF00766648