Dept. of Chemistry, Columbia University, 3000 Broadway, New York, NY 10027 (USA).
Dept. of Chemistry, The Scripps Research Institute, 130 Scripps Way, Jupiter, FL 33458 (USA) http://www.scripps.edu/snyder/index.htm.
Angew Chem Int Ed Engl. 2015 Jun 26;54(27):7842-6. doi: 10.1002/anie.201500925. Epub 2015 May 14.
Numerous natural products possess ring systems and functionality for which Hajos-Parrish ketone isomers with a transposed methyl group (termed "iso-Hajos-Parrish ketones") would be of value. However, such building blocks have not been exploited to the same degree as the more typical Hajos-Parrish hydrindane. An efficient three-step synthesis of such materials was fueled by a simple method for the rapid preparation of highly functionalized cyclopentenones, several of which are new chemical entities that would be challenging to access through other approaches. Furthermore, one iso-Hajos-Parrish ketone was converted into two distinct natural product analogues and one natural product. As one indication of the value of these new building blocks, that latter target was obtained in 10 steps, having previously been accessed in 18 steps using the Hajos-Parrish ketone.
许多天然产物都具有环系统和功能，而具有 trans 甲基取代基的 Hajos-Parrish 酮异构体（称为“iso-Hajos-Parrish 酮”）对此具有重要价值。然而，这些构建块并没有被充分利用，与更为典型的 Hajos-Parrish 氢化茚满相比更是如此。一种快速制备高官能化环戊烯酮的简单方法为这类材料的高效三步合成提供了动力，其中有几个是新的化学实体，通过其他方法难以获得。此外，一个 iso-Hajos-Parrish 酮被转化为两种不同的天然产物类似物和一种天然产物。作为这些新构建块价值的一个体现，该目标产物是通过 10 步反应得到的，而此前使用 Hajos-Parrish 酮则需要 18 步反应。
