Ando Yoshio, Hoshino Taiju, Tanaka Nozomi, Maturi Mark M, Nakazawa Yusuke, Fukazawa Takumi, Ohmori Ken, Suzuki Keisuke
Department of Chemistry, Tokyo Institute of Technology present name, Institute of Science Tokyo, 2-12-1 O-okayama, Meguro-ku, Tokyo, 152-8551, Japan.
Concurrent address of Emeritus Prof. Dr. K. Suzuki: The Kitasato Institute, Kitasato University, 5-9-1, Shirokane, Minato-ku, Tokyo, 108-8641, Japan.
Angew Chem Int Ed Engl. 2025 Feb 3;64(6):e202415108. doi: 10.1002/anie.202415108. Epub 2024 Nov 11.
After half a century from their isolation in 1974, we report the first total syntheses of β- and γ-naphthocyclinones, two dimeric pyranonaphthoquinones featuring an unusual bicyclo[3.2.1]octadienone core. The syntheses were achieved with full stereochemical control and functional group management, relying on 1) enantioselective construction of the bicyclic core by Rh-catalyzed enantioselective 1,4-addition followed by thiolate-mediated reductive cyclization, and 2) judicious design of a common chiral, non-racemic monomer unit that is capable of divergence into the donor and acceptor units, and reunion to construct the bicyclo[3.2.1]octadienone core.
在1974年分离出β-和γ-萘环素酮半个世纪后，我们报道了这两种具有不寻常双环[3.2.1]辛二烯酮核心的二聚吡喃萘醌的首次全合成。合成过程通过完全的立体化学控制和官能团调控得以实现，具体方法如下：1）通过铑催化的对映选择性1,4-加成反应构建双环核心，随后进行硫醇盐介导的还原环化反应，实现对映选择性构建双环核心；2）精心设计一个通用的手性、非外消旋单体单元，该单元能够分化为供体和受体单元，并重新结合以构建双环[3.2.1]辛二烯酮核心。
