論文 - 堤　亮祐

34 海産ポリ環状エーテル天然物の効率的全合成、ブレビシン(口頭発表の部)

倉永 健史, 大谷 真人, 堤 亮祐, 石原 周二, 佐竹 真幸, Wright Jeffrey L.C., 橘 和夫

天然有機化合物討論会講演要旨集 （天然有機化合物討論会）   （ 52 ） 199 - 204 2010年09月

研究論文（学術雑誌）, 共著, 査読有り

　概要を見る

A polycyclic ether bravisn (1) was isolated from the red tide dinoflagellate Karenia brevis, which produces a variety of policyclic ethers such as bervetoxins, brevenal, and a mono cyclic ether amide brevisamide. Its unique structure consists of two fused tricyclic ether ring assemblies bridged by a methylene carbon and a conjugated aldehyde side chain, which is similar to brevenal and breviasmide. Its separated polycyclic ether skeleton in the center of the molecule is unusual in the marine polycyclic ethers. Interestingly, even though its skeletal structure is divided into two tricyclic ether units by the methylene, brevisin inhibits the binding of tritiated 42-dihydrobrevetoxin B (PbTx-3) to the voltage sensitive sodium channels (VSSC). In order to confirm its aberrant chemical structure, elucidate its interation was essential. Here the total synthesis of brevisin based on highly convergent strategy using Suzuki-Miyaura cross coupling and aldol reaction as the key reactions was achieved in 29 steps (the longest linear sequence), and the datails will be reported in this presentation.

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SYNTHESIS OF THE ABC RING FRAGMENT OF BREVISIN, A NEW DINOFLAGELLATE POLYCYCLIC ETHER

Ohtani, Naohito and Tsutsumi, Ryosuke and Kuranaga, Takefumi and Shirai, Tomohiro and Wright, Jeffrey L. C. and Baden, Daniel G. and Satake, Masayuki and Tachibanaa, Kazuo

Heterocycles （Heterocycles）  80 （ 2 ） 825 - 830 2010年

研究論文（学術雑誌）, 共著, 査読有り,  ISSN  0385-5414

　概要を見る

渦鞭毛藻Karenia brevisより単離された天然物ブレビシンのABC環部分の合成を行った。

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An improved synthesis of (-)-brevisamide, a marine monocyclic ether amide of dinoflagellate origin

Tsutsumi, Ryosuke and Kuranaga, Takefumi and Wright, Jeffrey L. C. and Baden, Daniel G. and Ito, Emiko and Satake, Masayuki and Tachibana, Kazuo

Tetrahedron （Tetrahedron）  66 （ 34 ） 6775 - 6782 2010年

研究論文（学術雑誌）, 共著, 査読有り,  ISSN  0040-4020

　概要を見る

渦鞭毛藻Karenia brevisより単離された単環性エーテルアミド天然物ブレビサミドの合成を行い、合成標品の生物活性を評価した。

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P-43 ブレビサミドの全合成およひポリ環状エーテル化合物の生合成研究を目指した推定鎖状前駆体の合成(ポスター発表の部)

倉永 健史, 白井 智大, 堤 亮祐, 大谷 真人, Wright Jeffrey L.C., 佐竹 真幸, 橘 和夫

天然有機化合物討論会講演要旨集 （天然有機化合物討論会）   （ 51 ） 365 - 370 2009年09月

研究論文（学術雑誌）, 共著, 査読有り

　概要を見る

A red tide dinoflagellate Karenia brevis is known to produce polycyclic ethers such as the bravetoxins and brevenal. During isolation of these toxins, a new cyclic ether alkaloid named brevisamide (1) was isolated from laboratory cultured of K. brevis. The molecular formula of 1 was deduced to be C_<18>H_<29>NO_4 by HRMS and NMR spectral data. Based on 2D NMR analyses, brevisamide was found to possess a 3,4-dimethyl-2,4-heptadienal side-chain and an acetylated terminal amine. 1 is the first nitrogen-containing mono-cyclic ether from K. brevis and may provide important biogenetic clues to the origin and biosynthetic assembly of polyethers. Here we report the synthesis of 1 and its plausible biosynthetic precursors 2 and 3 supplying additional biological testing material for elucidation of biosynthetic mechanism of marine ladder-shaped polyethers.

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