Abstract
We report useful new lithium-assisted asymmetric anion-accelerated amino-Cope rearrangement cascades. A strategic nitrogen atom chiral auxiliary serves three critical roles, by (1) enabling in situ assembly of the chiral 3-amino-1,5-diene precursor, (2) facilitating the rearrangement via a lithium enolate chelate, and (3) imparting its influence on consecutive inter- or intramolecular C-C or C-X bond-forming events via resulting chiral enamide intermediates or imine products. The mechanism of the amino-Cope rearrangement was explored with density functional theory. A stepwise dissociation-recombination mechanism was found to be favored. The stereochemistry of the chiral auxiliary determines the stereochemistry of the Cope product by influencing the orientation of the lithium dienolate and sulfinylimine fragments in the recombination step. These robust asymmetric anion-accelerated amino-Cope enabled cascades open the door for rapid and predictable assembly of complex chiral acyclic and cyclic nitrogen-containing motifs in one pot.
Original language | English (US) |
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Pages (from-to) | 13141-13146 |
Number of pages | 6 |
Journal | Journal of the American Chemical Society |
Volume | 139 |
Issue number | 37 |
DOIs | |
State | Published - Sep 20 2017 |
Externally published | Yes |
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry
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CCDC 1451254: Experimental Crystal Structure Determination
Chogii, I. (Creator), Das, P. (Creator), Fell, J. S. (Creator), Scott, K. A. (Creator), Crawford, M. N. (Creator), Houk, K. N. (Creator) & Njardarson, J. T. (Creator), Cambridge Crystallographic Data Centre, 2017
DOI: 10.5517/ccdc.csd.cc1kq4n2, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1kq4n2&sid=DataCite
Dataset
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CCDC 1556649: Experimental Crystal Structure Determination
Chogii, I. (Creator), Das, P. (Creator), Fell, J. S. (Creator), Scott, K. A. (Creator), Crawford, M. N. (Creator), Houk, K. N. (Creator) & Njardarson, J. T. (Creator), Cambridge Crystallographic Data Centre, 2017
DOI: 10.5517/ccdc.csd.cc1p7th7, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1p7th7&sid=DataCite
Dataset