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 S_NAr 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.

中文翻译：

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全合成马洛图素。

描述了可乐宁的总合成，该物质在可乐宁上具有3,6- O-（R）-六羟基二苯甲酰基（HHDP）桥的葡萄糖的2-氧和4-氧之间带有四羟基二苯并呋喃酰基（THDBF）桥。总合成的关键特征是：1）改进了我们先前报道的合成丝胶的方法；2）通过HHDP类似物的异常分子内S _N Ar反应建立THDBF骨架，以及3）将HHDP桥构造成2,4- O- THDBF桥采用两步双内酯化策略。1,2,4-邻乙酰基-3-3,6-二（4-邻苄基加甲酰基）-α - d的氧化酚偶联葡萄糖吡喃糖和偶联产物的原酸酯裂解而不进行吡喃糖-呋喃糖环转化是改善可乐可宁合成的关键反应，可充分供应开发可乐宁的合成所需的可乐可宁前体。预期这些已建立的方法将有助于开发其他鞣花单宁的合成，其中鞣花单宁具有可乐宁的两个氧之间的桥。