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Published on: November 9, 2019
Regiodivergent (3 + 2) annulation reactions of oxyallyl cations
Zachary Protich1, Leah L Lowder1, Russell P Hughes1
1Department of Chemistry, Dartmouth College Hanover New Hampshire 03755 USA jimmy.wu@dartmouth.edu russell.p.hughes@dartmouth.edu.
Abstract:
We report a new method for the regiodivergent dearomative (3 + 2) reaction between 3-substituted indoles and oxyallyl cations. Access to both regioisomeric products is possible and is contingent on the presence or absence of a bromine atom on the substituted oxyallyl cation. In this way, we are able to prepare molecules that contain highly-hindered, stereodefined, vicinal, quaternary centers. Detailed computational studies employing energy decomposition analysis (EDA) at the DFT level establishes that regiochemical control arises from either reactant distortion energy or orbital mixing and dispersive forces, depending on the oxyallyl cation. Examination of the Natural Orbitals for Chemical Valence (NOCV) confirms that indole acts as the nucleophilic partner in the annulation reaction.
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