Quandt, G.; Brunnhofer, B.; Kapatsina, E.; Baron, J.; Fischer, A.;
Weymann, M.; Kunz, H. Angew. Chem. Int. Ed. 2009, 48, 2228.
(a) Berrien, J.–F.; Royer, J.; Husson, H.–P. J. Org. Chem. 1994, 59,
3769; (b) Guerrier, L.; Royer J.; Grierson, D. S.; Husson, H.–P. J. Am.
Chem. Soc. 1983, 105, 7754; (c) Maury, C.; Wang, Q.; Gharbaoui, T.;
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383. (e) CN (R,S) method allows the enantiodivergent synthesis by CN
elimination and the method is named in recognition of “Centre
National de la Recherche Scientifique”.
Acknowledgments
5.
R. G. B. thanks DST-SERB (EMR/2015/000909), Govt. of India
for the generous research grant. Authors also thank Indian
Institute of Science Education and Research (IISER), Pune for
the financial support. L.V. R. B. S. thanks CSIR-UGC and
IISER-P for the fellowship. Authors also thank Dr. Amar R.
Mohite for useful discussions.
6.
7.
(a) Royer, J.; Husson, H.–P. Heterocycles, 1993, 36, 1493; (b)
Munchhof, M. J.; Meyers, A. I. J. Am. Chem. Soc. 1995, 117, 5399; (c)
Meyers, A. I.; Brengel, G. P. Chem. Commun. 1997, 1.
Supplementary Material
(a) Bailey, P. D.; Wilson, R. D.; Brown, G. R.; J. Chem. Soc., Perkin
Trans. I 1991, 1337; (b) Bailey, P. D.; Brown, G. R.; Korber, F.; Reid,
A.; Wilson, R. D. Tetrahedron: Asymmetry, 1991, 2, 1263; (c) Grieco
P. A.; Parker, D. T. J. Org. Chem.1988, 53, 3325.
Experimental details, 1H, 13C NMR spectra and HPLC profiles
of compounds 6 are available in the supporting information.
8.
9.
(a) Comelles, J.; Moreno–Mañas, M.; Vallribera, A. ARKIVOC 2005,
(ix), 207; (b) Mohite, A. R.; Sultane, P. R.; Bhat, R. G. Tetrahedron
Lett. 2012, 53, 30. (c) L.-W. Xu, C.-G. Xia and X.-X. Hu, Chem.
Commun., 2003, 2570.
Various (L)–menthyl alkylidene β–keto esters 4 have been synthesized
starting from N-Boc β–alanine 2 which is in turn synthesized starting
from β–alanine 1 (see supporting information for the details).
References and notes
1.
(a) Braekman, J. C.; Daloze, D. In Studies in Natural Products
Chemistry, ‘Stereoselective Synthesis’, Part D: Atta–ur–Rahman, ed.;
Elsevier: Amsterdam, The Netherlands, 1990; Vol. 6, pp 421; (b)
Leclereq, S.; Braekman, J. C.; Daloze, D.; Pasteels, J. M.; Prog. Chem.
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Rep. 2000, 17, 579; (f) Michael, J. P. Nat. Prod. Rep. 2001, 18, 520.
For reviews on asymmetric syntheses of piperidines: See: (g) Meyers,
A. I.; Brengel, G. P.Chem. Commun. 1997, 1; (h) Bailey, P. D.;
Millwood, P. A.; Smith, P. D. Chem. Commun. 1998, 633; (i) Laschat,
S.; Dickner, T. Synthesis 2000, 13, 1781; (j) Mitchinson, A.; Nadin, A.
J. Chem. Soc., Perkin Trans. 1, 2000, 2862; (k) Groaning, M. D.;
Meyers, A. I. Tetrahedron 2000, 56, 9843; (l) Felpin, F.–X.; Lebreton,
J. Eur. J. Org. Chem. 2003, 3693; (m) Pearson, M. S. M.; Mathé–
Allainmat, M.; Fargeas, V.; Lebreton, J. Eur. J. Org. Chem. 2005,
2159; (n) Escolano, C.; Amat, M.; Bosch, J. Chem. Eur. J. 2006, 12,
8198; (o) Källström, S.; Leino, R. Bioorg. Med. Chem. 2008, 16, 601;
(p) Jørgensen, K. A. Angew. Chem., Int. Ed. 2000, 39, 3558; (q)
Nadin, A., Contemp. Org. Synth. 1997, 4, 387; (r) Buffat, M. G. P.
Tetrahedron 2004, 60, 1701.
10. Reaction containing both E and Z isomers (mixture) resulted in poor
stereoselectivity. Later, E and Z isomers were separated before the
1
reaction. Isolated E and Z isomers were confirmed H NMR and by 1d
nOe. Details and yields are given in supporting information.
11. Diastereomeric ratio was determined by HPLC. Chromatograms of all
the products (5a–5q) are given in supporting information.
12. A quick literature search revealed numerous examples of VTNMR or
other techniques being used for qualitative identification of rotamers
with no mention of saturation transfer; for a few examples, see: (a)
Myers, A. G.; Yang, B. H.; Chen, H.; McKinstry, L.; Kopecky, D. J.;
Gleason, J. L. J. Am. Chem. Soc. 1997, 119, 6496; (b) Dennis X. Hu,
Peter Grice, and Steven V. Ley, J. Org. Chem. 2012, 77, 5198; (c) Al–
Horani, R. A.; Desai, U. R. Tetrahedron 2012, 68, 2027; (d) Lewis, K.
C.; Maxwell, A. R.; McLean, S.; Reynolds, W. F.; Enriquez, R. G.
Magn. Reson. Chem. 2000, 38, 771; (e) Smith, A. B.; Chruma, J. J.;
Han, Q.; Barbosa, J. Bioorg. Med. Chem. Lett. 2004, 14, 1697; (f)
Dransfield, P. J.; Gore, P. M.; Prokes, I.; Shipman, M.; Slawin, A. M.
Z. Org. Biomol. Chem. 2003, 1, 2723.
2.
3.
O’Hagan, D. Nat. Prod. Rep. 2000, 17, 435.
(a) Baumann, M.; Baxendale, I. R. Beilstein J. Org.
Chem. 2013, 9, 2265; (b) Watson, P. S.; Jiang, B. Org. Lett. 2000, 2,
3679. (c) Jayabharathi, J.; Manimekalai, A.; Vani, T. C.; Padmavathy,
M. Eur. J. Med. Chem. 2007, 42, 593; (d) Harini, S. T.; Kumar, H. V.;
Rangaswamy, J.; Naik, N. Bioorg. Med. Chem. Lett. 2012, 22, 7588.
Bailey, P. D.; Millwood, P. A.; Smith, P. D. Chem. Commun. 1998,
633; b) Davis, F. A.; Chao, B.; Rao, A. Org. Lett. 2001, 3, 3169; c)
Davis, F. A.; Zhang, J.; Li, Y.; Xu, H.; DeBrosse, C. J. Org. Chem.
2005, 70, 5413; d) Semina, E.; Colpaert, F.;Hecke, K. V.; Kimpe, N.
D.; Mangelinckx, S. Eur. J. Org. Chem. 2015, 4847; e) Stoye, A.;
13. It was difficult to calculate the exact yield of both diastereomers as
some amount of diastereomers was isolated as mixture. Hence, the
combined yields of the diastereomers are reported.
14. Purity of piperidine hydrochloride salts (6) has been confirmed by
HPLC studies and they were found to be highly pure (up to 99%, see
ESI). [(-)-Menthol of 99% ee purity was used for the reactions]
4.
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