Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
Faculty of Pharmaceutical Sciences, Hokkaido University, Kita-ku, Sapporo, 060-0812, Japan.
Angew Chem Int Ed Engl. 2017 Jun 12;56(25):7156-7160. doi: 10.1002/anie.201703193. Epub 2017 May 16.
A highly atom economical and stereoselective synthesis of tetrasubstituted α,β-unsaturated amides was achieved by a CpCo -catalyzed C-H alkenylation/directing group migration sequence. A carbamoyl directing group, which is typically removed after C-H functionalization, worked as an internal acylating agent and migrated onto the alkene moiety of the product. The directing group migration was realized with the CpCo catalyst, while a related Cp*Rh catalyst did not promote the migration process. The product was further converted into two types of tricyclic compounds, one of which had fluorescent properties.
通过 CpCo 催化的 C-H 烯化/导向基团迁移序列，实现了四取代的α,β-不饱和酰胺的高原子经济性和立体选择性合成。通常在 C-H 官能化后去除的氨甲酰基导向基团作为内部酰化剂，并迁移到产物的烯烃部分。导向基团迁移是由 CpCo 催化剂实现的，而相关的 Cp*Rh 催化剂则不促进迁移过程。该产物进一步转化为两种类型的三环化合物，其中一种具有荧光性质。
