Enantioselective Catalysis of the Aza-Cope Rearrangement by a Chiral Supramolecular Assembly

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The chiral supramolecular catalyst Ga{sub 4}L{sub 6} [L = 1,5-bis(2,3-dihydroxybenzoylamino)naphthalene] is a molecular tetrahedron that catalyzes the 3-aza-Cope rearrangement of allyl enammonium cations. This catalysis is accomplished by preorganizing the substrate in a reactive conformation within the host. This work demonstrates that through the use of enantiopure assembly, its chiral cavity is capable of catalyzing the 3-aza-Cope rearrangement enantioselectively, with yields of 21-74% and enantiomeric excesses from 6 to 64% at 50 C. At lower temperatures, the enantioselectivity improved, reaching 78% ee at 5 C. This is the highest enantioselectivity to date induced by the chiral cavity of a supramolecular ... continued below

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Brown, Casey J.; Bergman, Robert G. & Raymond, Kenneth N. July 29, 2009.

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The chiral supramolecular catalyst Ga{sub 4}L{sub 6} [L = 1,5-bis(2,3-dihydroxybenzoylamino)naphthalene] is a molecular tetrahedron that catalyzes the 3-aza-Cope rearrangement of allyl enammonium cations. This catalysis is accomplished by preorganizing the substrate in a reactive conformation within the host. This work demonstrates that through the use of enantiopure assembly, its chiral cavity is capable of catalyzing the 3-aza-Cope rearrangement enantioselectively, with yields of 21-74% and enantiomeric excesses from 6 to 64% at 50 C. At lower temperatures, the enantioselectivity improved, reaching 78% ee at 5 C. This is the highest enantioselectivity to date induced by the chiral cavity of a supramolecular assembly.

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17530

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  • Journal Name: Journal of the American Chemical Society; Journal Volume: 131; Journal Issue: 48

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  • Report No.: LBNL-2886E
  • Grant Number: DE-AC02-05CH11231
  • DOI: 10.1021/ja906386w | External Link
  • Office of Scientific & Technical Information Report Number: 993492
  • Archival Resource Key: ark:/67531/metadc1016081

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  • July 29, 2009

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  • Oct. 14, 2017, 8:36 a.m.

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  • Oct. 17, 2017, 8:13 p.m.

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Brown, Casey J.; Bergman, Robert G. & Raymond, Kenneth N. Enantioselective Catalysis of the Aza-Cope Rearrangement by a Chiral Supramolecular Assembly, article, July 29, 2009; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc1016081/: accessed December 13, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.