Sun Xin, Gao Peng-Chao, Sun Yu-Wen, Li Bi-Jie
Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing 100084, China.
State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China.
J Am Chem Soc. 2024 Jan 10;146(1):723-732. doi: 10.1021/jacs.3c10609. Epub 2023 Dec 20.
Despite the current progress achieved in asymmetric hydroacylations, highly enantioselective catalytic addition of unfunctionalized aldehydes to internal alkenes remains an unsolved challenge. Here, using a coordination-assisted strategy, we developed a rhodium-catalyzed regio- and enantioselective addition of unfunctionalized aldehydes to internal alkenes such as enamides and β,γ-unsaturated amides. Valuable α-amino ketones and 1,4-dicarbonyl compounds were directly obtained with high enantioselectivity from readily available materials.
尽管目前在不对称氢酰化反应中取得了进展，但未官能团化醛与内烯烃的高对映选择性催化加成仍然是一个未解决的挑战。在此，我们采用配位辅助策略，开发了一种铑催化的未官能团化醛与内烯烃（如烯酰胺和β,γ-不饱和酰胺）的区域和对映选择性加成反应。从易得的原料直接获得了具有高对映选择性的有价值的α-氨基酮和1,4-二羰基化合物。
