Total Synthesis of Marchantinquinone 英文参考文献.docVIP

334 Molecules 2000, 5 Total Synthesis of Marchantinquinone V. López, E. Pandolfi and G. Seoane Cátedra de Química Orgánica. Facultad de Química. Universidad de la República. Gral. Flores 2124. C.C. 1157. C.P. 11800. Montevideo, Uruguay E-mail: vlopez@bilbo.edu.uy Abstract. During the last years, many bisbibenzylic macrocyclic ethers were isolated and identified in Hepaticae. One of them is MARCHANTINQUINONE, a quinonic macrocycle with interesting biological activity. In the following report, we present the last steps of the total synthesis. Introduction Bisbibenzylic systems such as Marchantins, Perrottetins, Riccardins are found only in Hepatica and have been shown to display a wide range of biological activities [1,2]. Marchantinquinone (1), from extracts of Reboulia hemisphaerica, formerly described as Mannia subpilosa, [3,4] was the first bisbibenzylic diether possessing a quinone structure isolated from Bryophytes. Herein its first synthe- sis is reported. Experimental Relevant steps of the synthesis are shown in the following retrosynthetic scheme: O O O OH C OCH3 C OCH3 A A A C COOCH3 O OCH3 H3CO O H3CO OH B O O O D D A C B B OCH3 OCH3 MARCHANTINQUINONE 1 2 3 COOCH3 CHO 4 The global strategy of this synthesis is based on standard organic synthesis reactions: nucleophilic aromatic substitution, Wittig reaction, catalytic hydrogenation. It also includes redox reactions and  335 Molecules 2000, 5 macrocyclization using Nio complex. Results and Discussion Previously, we described the synthesis of macrocycle (2) [5] an advance precursor of Marchantin- quinone (1). Different conditions of macrocyclization, deprotection and oxidation to obtain the qui- nonic structure will be disclosed. O O O OCH3 C OCH3 C OH C A A A [Ni0] BBr3/CH2Cl2 CH2Cl [O] CH2Cl 1 H3CO H3CO HO O D O D B O D B B OCH3 OCH3 OH 5 2 6 References and Notes 1. 2. Zinsmeister, H.D.; Becker, H.; Eicher, Th. Angew. Chem. 1991, 103, 134.