Divergent Catalysis: Catalytic Asymmetric [4+2] Cycloaddition of Palladium Enolates
Kaylin N. Flesch, Alexander Q. Cusumano, Peng-Jui Chen, Christian Santiago Strong, Stephen R. Sardini, Yun E. Du, Michael D. Bartberger, William A. Goddard III, Brian M. Stoltz
2023J. Am. Chem. Soc., 145(20), 11301-1131012cited
Abstract
An asymmetric decarboxylative [4+2] cycloaddition from a catalytically generated chiral Pd enolate was developed, forging four contiguous stereocenters in a single transformation. This was achieved through a strategy termed divergent catalysis, wherein departure from a known catalytic cycle enables novel reactivity of a targeted intermediate prior to re-entry into the original cycle. Mechanistic studies including quantum mechanics calculations, Eyring analysis, and KIE studies offer insight into the reaction mechanism.
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Flesch, K. N., Cusumano, A. Q., Chen, P., Strong, C. S., Sardini, S. R., Du, Y. E., Bartberger, M. D., III, W. A. G., & Stoltz, B. M. (2023). Divergent Catalysis: Catalytic Asymmetric [4+2] Cycloaddition of Palladium Enolates. *J. Am. Chem. Soc.*, *145*(20), 11301-11310. https://doi.org/10.1021/jacs.3c02104