This work discloses the first examples of an effective enantioselective oxy‐Heck–Matsuda reaction using a variety of styrenic olefins to generate chiral dihydrobenzofurans. The reaction proceeds in moderate to good yields, with high trans diastereoselectivity (up to 20:1) in enantioselectivities up to 90:10 using the N,N‐ligand pyrimidine‐bisoxazoline (PyriBox). The oxy‐Heck–Matsuda reactions were carried out under mild conditions and rather low catalyst loadings. The feasibility and practicality of the process is demonstrated by a concise total synthesis of the neolignan (−)‐conocarpan. X‐ray diffraction of an advanced brominated intermediate in the route to (−)‐conocarpan has allowed the unequivocal assignment of the absolute stereochemistry of the oxy‐Heck–Matsuda aryldihydrobenzofuran products. A rationale for the mechanism operating in these enantioselective oxy‐Heck–Matsuda reactions is also presented.

中文翻译：

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对映选择性Oxy-Heck-Matsuda芳基化：二氢苯并呋喃系统的快速合成和新木脂素（-）-Conocarpan的全合成

这项工作公开了使用多种苯乙烯烯烃生成手性二氢苯并呋喃的有效对映选择性氧-Heck-Matsuda反应的第一个实例。该反应以中等至良好的产率进行，具有高反式使用N，N-配体嘧啶-双恶唑啉（PyriBox）在90:10的对映选择性中具有非对映选择性（高达20：1）。oxy-Heck-Matsuda反应在温和的条件下和较低的催化剂载量下进行。新木脂素（-）-角果胶的简明全合成证明了该方法的可行性和实用性。在通往（-）-香柏树醇的途径中，对高级溴化中间体进行X射线衍射分析，使得对氧-赫克-松田芳基二氢苯并呋喃产品的绝对立体化学的明确分配成为可能。还介绍了在这些对映选择性氧-Heck-Matsuda反应中起作用的机理的基本原理。