Stereo-Differentiating Asymmetric Rh(I)-Catalyzed Pauson–Khand Reaction: A DFT-Informed Approach to Thapsigargin Stereoisomers,Journal of the American Chemical Society

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Stereo-Differentiating Asymmetric Rh(I)-Catalyzed Pauson–Khand Reaction: A DFT-Informed Approach to Thapsigargin Stereoisomers
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-12-19 , DOI: 10.1021/jacs.4c11661
Fatemeh Haghighi, Luke T. Jesikiewicz, Corrinne E. Stahl, Jordan Nafie, Amanda Ortega-Vega, Peng Liu, Kay M. Brummond

We report a stereo-differentiating dynamic kinetic asymmetric Rh(I)-catalyzed Pauson–Khand reaction, which provides access to an array of thapsigargin stereoisomers. Using catalyst-control, a consistent stereochemical outcome is achieved at C2─for both matched and mismatched cases─regardless of the allene-yne C8 stereochemistry. The stereochemical configuration for all stereoisomers was assigned by comparing experimental vibrational circular dichroism (VCD) and ¹³C NMR to DFT-computed spectra. DFT calculations of the transition-state structures corroborate experimentally observed stereoselectivity and identify key stabilizing and destabilizing interactions between the chiral ligand and allene-yne PKR substrates. The robust nature of our catalyst-ligand system places the total synthesis of thapsigargin and its stereoisomeric analogues within reach.

更新日期：2024-12-20

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