Sennari Goh, Yamagishi Hiroki, Sarpong Richmond
Department of Chemistry, University of California, Berkeley, California 94720, United States.
O̅mura Satoshi Memorial Institute and Graduate School of Infection Control Sciences, Kitasato University, 5-9-1 Shirokane, Minato-ku, Tokyo 108-8641, Japan.
J Am Chem Soc. 2024 Mar 20;146(11):7850-7857. doi: 10.1021/jacs.4c01351. Epub 2024 Mar 6.
Camphor continues to serve as a versatile chiral building block for chemical synthesis. We have developed a novel method to functionalize the camphor skeleton at C8 using an intramolecular hydrogen atom abstraction. The key advance involves the use of a camphor-derived aminonitrile, which is converted to the corresponding nitrogen-centered radical under photoredox conditions to effect the 1,5-hydrogen atom transfer at C8. The resulting carbon-centered radical at C8 was utilized in a C-H amination to access topologically complex proline derivatives. Furthermore, the total synthesis of several sesquiterpenoids was accomplished by engaging the radical generated at C8 in alkylation reactions.
樟脑仍然是化学合成中一种多功能的手性结构单元。我们开发了一种新颖的方法，通过分子内氢原子提取来官能化樟脑骨架的C8位。关键进展包括使用樟脑衍生的氨基腈，其在光氧化还原条件下转化为相应的以氮为中心的自由基，以实现C8位的1,5-氢原子转移。在C-H胺化反应中利用C8位生成的以碳为中心的自由基来获得拓扑结构复杂的脯氨酸衍生物。此外，通过使C8位生成的自由基参与烷基化反应，完成了几种倍半萜类化合物的全合成。
