Journal of the American Chemical Society
Communication
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In summary, we have developed an enantioconvergent kinetic
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bicyclo[3.1.0]hexenes that has not been shown to be possible
with gold(I). This transformation represents a rare mode of
direct enantioconvergent kinetic resolution wherein product
enantioenrichment is increased at synthetically useful con-
versions and starting material enantioenrichment is maintained
when compared to a standard kinetic resolution. More
importantly, these transformations mark the first highly
enantioselective reactions catalyzed by a well-defined gold(III)
complex and set the stage for further exploration and
development.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
■
S
Experimental details and characterization data (PDF)
Crystallographic data for 3 (CIF)
(7) (a) Wu, C.; Horibe, T.; Jacobsen, C. B.; Toste, F. D. Nature 2015,
517, 449−454. See also: (b) Joost, M.; Estevez, L.; Miqueu, K.;
́
AUTHOR INFORMATION
Corresponding Author
■
Amgoune, A.; Bourissou, D. Angew. Chem., Int. Ed. 2015, 54, 5236−
5240. (c) For an early example of organometallic diarylgold(III)
catalysts, see: Casado, R.; Contel, M.; Laguna, M.; Romero, P.; Sanz, S.
J. Am. Chem. Soc. 2003, 125, 11925−11935.
ORCID
Notes
The authors declare no competing financial interest.
(8) (a) Luzung, M. R.; Markham, J. P.; Toste, F. D. J. Am. Chem. Soc.
2004, 126, 10858−10859. (b) For a related gold-catalyzed reaction of
hydroxylated enynes, see: Mamane, V.; Gress, T.; Krause, H.; Furstner,
̈
A. J. Am. Chem. Soc. 2004, 126, 8654−8655. (c) For the platinum-
catalyzed variant, see: Harrak, Y.; Blaszykowski, C.; Bernard, M.;
Cariou, K.; Mainetti, E.; Mouries, V.; Dhimane, A.-L.; Fensterbank, L.;
Malacria, M. J. Am. Chem. Soc. 2004, 126, 8656−8657.
ACKNOWLEDGMENTS
■
We gratefully acknowledge NIGMS (R35 GM118190) for
financial support. We thank Dr. Mark Levin, Andrew Samant,
Dr. Johnathan Brantley, and Dr. Steven Jacob for helpful
discussions, Xingyu Jiang for SFC assistance, and Richard
Thornbury and Nicholas Settineri for X-ray crystallography
assistance.
(9) Enantioselective gold(I) catalyzed cycloisomerization reactions of
(a) hydroxylated 1,5-enynes: Wu, Z.; Retailleau, P.; Gandon, V.;
Voituriez, A.; Marinetti, A. Eur. J. Org. Chem. 2016, 2016, 70−75. (b)
1,5-silyloxyenynes: Brazeau, J. F.; Zhang, S.; Colomer, I.; Corkey, B. K.;
Toste, F. D. J. Am. Chem. Soc. 2012, 134, 2742−2749.
(10) Patil, N. T. Chem. - Asian J. 2012, 7, 2186−2194.
(11) For examples of enantioselective catalysis with chiral
NHCgold(I) complexes, see: (a) Strand, R. B.; Helgerud, T.;
Solvang, T.; Dolva, A.; Sperger, C. A.; Fiksdahl, A. Tetrahedron:
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