156700-98-0Relevant articles and documents
Photoinduced Copper-Catalyzed Asymmetric C-O Cross-Coupling
Chen, Jun,Liang, Yu-Jie,Wang, Peng-Zi,Li, Guo-Qing,Zhang, Bin,Qian, Hao,Huan, Xiao-Die,Guan, Wei,Xiao, Wen-Jing,Chen, Jia-Rong
supporting information, p. 13382 - 13392 (2021/09/03)
The construction of carbon-heteroatom bonds is one of the most active areas of research in organic chemistry because the function of organic molecules is often derived from the presence of heteroatoms. Although considerable advances have recently been achieved in radical-involved catalytic asymmetric C-N bond formation, there has been little progress in the corresponding C-O bond-forming processes. Here, we describe a photoinduced copper-catalyzed cross-coupling of readily available oxime esters and 1,3-dienes to generate diversely substituted allylic esters with high regio- and enantioselectivity (>75 examples; up to 95% ee). The reaction proceeds at room temperature under excitation by purple light-emitting diodes (LEDs) and features the use of a single, earth-abundant copper-based chiral catalyst as both the photoredox catalyst for radical generation and the source of asymmetric induction in C-O coupling. Combined experimental and density functional theory (DFT) computational studies suggest the formation of π-allylcopper complexes from redox-active oxime esters as bifunctional reagents and 1,3-dienes through a radical-polar crossover process.
Bioinspired intramolecular diels-alder reaction: A rapid access to the highly-strained cyclopropane-fused polycyclic skeleton
Zhu, Shifa,Guo, Zhengjiang,Huang, Zhipeng,Jiang, Huanfeng
supporting information, p. 2425 - 2430 (2014/03/21)
A bioinsipred gold-catalyzed tandem Diels-Alder/Diels-Alder reaction of an enynal and a 1,3-diene, forming the highly-strained benzotricyclo[3.2.1.0 2,7]octane skeleton, was reported. In contrast, a Diels-Alder/Friedel-Crafts tandem reaction occurred instead when silver salts were used as the catalyst. Although both reactions experienced the similar Diels-Alder reaction of a pyrylium intermediate with a 1,3-diene, they have different reaction mechanisms. The former proceeded with a stepwise Diels-Alder reaction, while the latter one with a concerted one. Mother nature knows best! A gold-catalyzed reaction of enynals and 1,3-dienes, giving rapid access to the highly strained benzotricyclo[3.2.1.02,7]octane skeleton, is reported (see scheme; QMD=quinodimethane). Owing to the mild reaction conditions, excellent substrate scope, and high functional-group tolerance, this system holds potential for the construction of complex molecules with the tricyclo[3.2.1.02,7]octane skeleton. Copyright
