Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, School of Petrochemical Engineering, Changzhou University, 1 Gehu Road, 213164, Changzhou, China.
Nat Commun. 2022 Jun 7;13(1):3146. doi: 10.1038/s41467-022-30846-y.
The Nazarov cyclization is one of the most powerful tools for the stereoselective synthesis of various cyclopentenone scaffolds. Therefore, developing the new classes substrate of Nazarov reaction is an important endeavor in synthetic chemistry. Herein, we report enyne diketones, enables diastereo- and enantioselective construction of chiral allene cyclopentenones in moderate to good yields with good enantioselectivities (up to 97% ee). Importantly, it is a typical example for asymmetric synthesis of cyclopentanones with allene moiety using Nazarov cyclisation. Mechanistic studies indicate that this metal-organo relay catalysis protocol involves a rhodium-catalyzed tandem oxonium ylide formation/[2,3]-sigmatropic rearrangement/reverse benzylic acid rearrangement, followed by organo-catalyzed asymmetric Nazarov cyclization/alkyne-to-allene isomerization to give the final chiral allene cyclopentenones.
纳扎罗夫环化反应是立体选择性合成各种环戊烯酮支架的最有力工具之一。因此，开发纳扎罗夫反应的新型底物类是合成化学中的一个重要努力。在此，我们报告了烯炔二酮，它能够以中等至良好的收率和良好的对映选择性（高达 97%ee）实现手性烯丙基环戊烯酮的非对映和对映选择性构建。重要的是，它是使用纳扎罗夫环化反应不对称合成具有烯丙基部分的环戊酮的典型例子。机理研究表明，这种金属-有机接力催化方案涉及铑催化的串联氧𬭩叶立德形成/[2,3]-西格玛重排/反苄基酸重排，然后进行有机催化的不对称纳扎罗夫环化/炔烃-烯丙基异构化，得到最终的手性烯丙基环戊烯酮。
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