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Open Access Publications from the University of California

Strategies for remote enantiocontrol in chiral gold(iii) complexes applied to catalytic enantioselective γ,δ-Diels-Alder reactions.

  • Author(s): Reid, Jolene P;
  • Hu, Mingyou;
  • Ito, Susumu;
  • Huang, Banruo;
  • Hong, Cynthia M;
  • Xiang, Hengye;
  • Sigman, Matthew S;
  • Toste, F Dean
  • et al.

The use of chiral square planar gold(iii) complexes to access enantioenriched products has rarely been applied in asymmetric catalysis. In this context, we report a mechanistic and synthetic investigation into the use of N-heterocyclic (NHC) gold(iii) complexes in γ,δ-Diels-Alder reactions of 2,4-dienals with cyclopentadiene. The optimal catalyst bearing a unique 2-chloro-1-naphthyl substituent allowed efficient synthesis of functionally rich carbocycles in good yields, diastereo- and enantioselectivities. Transition state and multivariate linear regression (MLR) analysis of both catalyst and substrate trends using molecular descriptors derived from designer parameter acquisition platforms, reveals attractive non-covalent interactions (NCIs) to be key selectivity determinates. These analyses demonstrate that a putative π-π interaction between the substrate proximal double bond and the catalyst aromatic group is an essential feature for high enantioselectivity.

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