Organic Letters
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imidazolidinone derivative 3 that exists exclusively in the cis-
fused form was designed. This bicyclic system imparts
complete diastereoselectivity in the N-quaternization with
allylic electrophiles, and this diastereomeric purity was
completely transferred via a diastereoselective [2,3]-Stevens
rearrangement to give enantiomerically enriched Cα-tetrasub-
stituted proline derivatives. Overall, the chiral information on
the original α-carbon of proline is perfectly transmitted to the
adjacent nitrogen center and transferred back to the original
carbon center via the rigid bicyclic proline system, which is
unique compared to other asymmetric syntheses of Cα-
tetrasubstituted prolines from proline itself. Applications of this
method in the synthesis of other natural products and bioactive
compounds are in progress and will be reported in due course.
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ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
(11) For selected reports on nitrogen inversion in nitrogen-bridged
bicycle, see: (a) Nelsen, S. F.; Ippoliti, J. T.; Frigo, T. B.; Petillo, P. A.
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Experimental procedures, analytical data, and copies of
1
the H and 13C NMR spectra for all new products
Accession Codes
mentary crystallographic data for this paper. These data can be
contacting The Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
(14) (a) Seebach, D.; Beck, A. K.; Badine, D. M.; Limbach, M.;
Eschenmoser, A.; Treasurywala, A. M.; Hobi, R.; Prikoszovich, W.;
́
Linder, B. Helv. Chim. Acta 2007, 90, 425. (b) Sanchez, D.; Castro-
Alvarez, A.; Vilarrasa, J. Tetrahedron Lett. 2013, 54, 6381.
(15) For selected reports on stereoselective Cα-alkylations of
imidazolidinone derivatives, see: (a) Knight, B. J.; Stache, E. E.;
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Ferreira, E. M. Tetrahedron 2015, 71, 5814.
AUTHOR INFORMATION
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Corresponding Author
ORCID
(16) For selected reports on asymmetric [2,3] rearrangements of
ammonium salts, see: (a) Workman, J. A.; Garrido, N. P.; Sancon, J.;
Roberts, E.; Wessel, H. P.; Sweeney, J. B. J. Am. Chem. Soc. 2005, 127,
1066. (b) Blid, J.; Panknin, O.; Somfai, P. J. Am. Chem. Soc. 2005,
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12956. (d) West, T. H.; Daniels, D. S. B.; Slawin, A. M. Z.; Smith, A.
D. J. Am. Chem. Soc. 2014, 136, 4476. (e) Tayama, E.; Naganuma, N.;
Iwamoto, H.; Hasegawa, E. Chem. Commun. 2014, 50, 6860. (f) West,
T. H.; Spoehrle, S. S. M.; Kasten, K.; Taylor, J. E.; Smith, A. D. ACS
Catal. 2015, 5, 7446.
(17) Hinds, M. G.; Welsh, J. H.; Brennand, D. M.; Fisher, J.;
Glennie, M. J.; Richards, N. G. J.; Turner, D. L.; Robinson, J. A. J.
Med. Chem. 1991, 34, 1777.
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preference of the endo transition state during the [2,3]-rearrange-
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This work was supported by the Mid-Career Researcher
Program (Grant No. NRF-2016R1A2A1A05005375) of the
National Research Foundation of Korea (NRF) funded by the
Government of Korea (MSIP).
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