Palladium-Catalyzed Asymmetric Cycloaddition/Cope Rearrangement Relay: Synthesis of Chiral Endocyclic Allenes
Bin Shi
a
CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, P. R. of China
,
Wen-Jing Xiao
a
CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, P. R. of China
,
Liang-Qiu Lu∗
a
CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, P. R. of China
b
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou, Gansu 730000, P. R. of China
b
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, P. R. of China
› Author AffiliationsThis work was supported by National Natural Science Foundation of China (No. 22271113, 92256301, 21820102003 and 91956201), the Hubei International Scientific and Technological Cooperation Base of Pesticide and Green Synthesis, and the Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction (Ministry of Education).
The synthesis of chiral endocyclic allenes, especially the medium-sized ones, remains a challenge in allene chemistry due to unfavorable tension and difficult stereocontrol. Herein, an efficient protocol for the construction of chiral nine-membered endocyclic allenes via palladium-catalyzed asymmetric cycloaddition/Cope rearrangement relay of vinyl carbonates with activated enynes is highlighted. This process provides rapid access to a variety of chiral nine-membered endocyclic allenes in good yields with excellent enantioselectivities. In particular, a chiral P,S-ligand shows good performance on stereoinduction, generating central and axial chirality in a single transformation, which is rationalized by DFT calculations and by a proposed transition state.
24 CCDC 2122960 contains the supplementary crystallographic data for compound 4da. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures