Uncovering Subtle Ligand Effects of Phosphines Using Gold(I) Catalysis
- Author(s): Christian, AH
- Niemeyer, ZL
- Sigman, MS
- Toste, FD
- et al.
Published Web Locationhttps://doi.org/10.1021/acscatal.7b00757
© 2017 American Chemical Society. Herein, we report the integration of simple linear regressions with gold(I) catalysis to interrogate the influence of phosphine structure on metal-catalyzed organic transformations. We demonstrate that observed product ratios in [4 + 3]/[4 + 2] cycloisomerization processes are influenced by both steric and electronic properties of the phosphine, which can be represented by the Au-Cl distance. In contrast, the observed selectivity of a similar [2 + 3]/[2 + 2] cycloisomerization is governed by L/B1, a steric parameter. Using this correlation, we were able to accurately predict the selectivity of a previously untested, Buchwald-type ligand to enhance selectivity for the same transformation. This ligand found further utility in increasing the selectivity of a previously reported gold-catalyzed cycloisomerization/arylation of 1,6-enynes by ∼1 kcal/mol.
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