Total Synthesis of Mallotusinin |
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Authors: | Kohei Yamashita Yuji Kume Seiya Ashibe Cicilia A. D. Puspita Kotaro Tanigawa Naoki Michihata Prof. Dr. Shinnosuke Wakamori Prof. Dr. Kazutada Ikeuchi Prof. Dr. Hidetoshi Yamada |
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Affiliation: | School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, 669-1337 Japan |
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Abstract: | The total synthesis of mallotusinin, which bears a tetrahydroxydibenzofuranoyl (THDBF) bridge between the 2-oxygen and 4-oxygen of glucose on corilagin with a 3,6-O-(R)-hexahydroxydiphenoyl (HHDP) bridge, is described. The key features of the total synthesis are: 1) improvements of our previously reported method to synthesize corilagin; 2) establishment of the THDBF skeleton via an unusual intramolecular SNAr reaction of an HHDP analogue, and 3) the application of a two-step bislactonization strategy for a HHDP bridge construction into the 2,4-O-THDBF bridge. Oxidative phenol coupling of 1,2,4-orthoacetyl-3,6-di-(4-O-benzylgalloyl)-α-d -glucopyranose and the orthoester cleavage of the coupling product without the pyranose-furanose ring transformation are key reactions for the improved synthesis of corilagin, which enabled the adequate supply of a corilagin precursor that was required to develop the mallotusinin synthesis. These established methods are expected to help develop the synthesis of other ellagitannins with a bridge between the two oxygens of corilagin. |
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Keywords: | natural products total synthesis intramolecular SNAr reactions lactones |
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