Concise and Stereodivergent Approach to Chromanone Lactones through Copper‐Catalyzed Asymmetric Vinylogous Addition of Siloxyfurans to 2‐Ester‐Substituted Chromones
Concise and Stereodivergent Approach to Chromanone Lactones through Copper‐Catalyzed Asymmetric Vinylogous Addition of Siloxyfurans to 2‐Ester‐Substituted Chromones
复制标题
通过铜催化硅氧基呋喃与 2-酯取代色酮的不对称乙烯加成得到色满酮内酯的简洁且立体发散的方法
DOI：
10.1002/anie.202203128
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Masakatsu Shibasaki
中科院分区：
文献类型：
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作者：
Jin Cui;Raphael Oriez;Hidetoshi Noda;Takumi Watanabe;Masakatsu Shibasaki
邻位含氧的四取代和三取代立体中心广泛存在于色满酮内酯和四羟基蒽酮天然产物中。它们的对映选择性结构在一个单一的步骤仍然是难以捉摸的，并提出了一个艰巨的挑战，化学合成。在这里，我们报告了第一个铜（I）催化的不对称乙烯基加成的2-酯取代的色酮，这使得简洁和对映选择性组装的色满酮内酯。通过明智地选择手性配体，可以以优异的非对映体和对映体选择性获得顺式加合物和反式加合物。我们的方法允许在精确的立体化学控制下有效合成（-）-blennalone B，这提供了secalonic酸A的正式合成。
Vicinal oxygen‐containing tetra‐ and tri‐substituted stereocenters exist widely in chromanone lactone and tetrahydroxanthone natural products. Their enantioselective construction in a single step remains elusive and poses a formidable challenge for chemical synthesis. Here, we report the first copper(I)‐catalyzed asymmetric vinylogous additions of siloxyfurans to 2‐ester‐substituted chromones, which enable concise and enantioselective assembly of chromanone lactones. Bothsynandantiadducts can be accessed with excellent diastereo‐ and enantioselectivity by judicious choice of the chiral ligands. Our approach allowed for the efficient synthesis of (−)‐blennolide B with precise stereochemical control, which provides a formal synthesis of secalonic acid A.