Organic Letters
Letter
Notes
Scheme 2. Scale-Up Experiment and Post-functionalization
Reactions
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
̀
This work was supported by the Ministere de l’Education
Nationale, de l’Enseignement Superieur et de la Recherche
́
(MENESR) and the Centre National de la Recherche
Scientifique (CNRS). We gratefully acknowledge the China
Scholarship Council (CSC) for a grant to L.-S. Z. We thank G.
́
Gontard for the X-ray analysis (Sorbonne Universite, Paris).
REFERENCES
■
(1) Hernandes, M. Z.; Cavalcanti, S. M. T.; Moreira, D. R. M.; de
Azevedo, W. F., Jr.; Leite, A. C. L. Curr. Drug Targets 2010, 11, 303.
(2) Wilcken, R.; Zimmermann, M. O.; Lange, A.; Joerger, A. C.;
Boeckler, F. M. J. Med. Chem. 2013, 56, 1363.
(3) (a) Yamamoto, T.; Ishibuchi, S.; Ishizuka, T.; Haratake, M.;
Kunieda, T. J. Org. Chem. 1993, 58, 1997. (b) Pinho, P.; Kalayanov,
̈
G.; Westerlind, H.; Rosenquist, Å.; Wahling, H.; Sund, C.; Almeida,
M.; Ayesa, S.; Tejbrant, J.; Targett-Adams, P.; Eneroth, A.; Lindqvist,
A. Bioorg. Med. Chem. Lett. 2017, 27, 3468. (c) Miller, E. J.; Mays, S.
G.; Baillie, M. T.; Howard, R. B.; Culver, D. G.; Saindane, M.; Pruett,
S. T.; Holt, J. J.; Menaldino, D. S.; Evers, T. J.; Reddy, G. P.;
Arrendale, R. F.; Natchus, M. G.; Petros, J. A.; Liotta, D. C. ACS Med.
Chem. Lett. 2016, 7, 537. (d) Si, C.; Fales, K. R.; Torrado, A.;
Frimpong, K.; Kaoudi, T.; Vandeveer, H. G.; Njoroge, F. G. J. Org.
Chem. 2016, 81, 4359.
(4) (a) Kaneda, T.; Komura, S.; Kitazume, T. J. Fluorine Chem. 2005,
126, 17. (b) Zhou, H.; Xu, Q.; Chen, P. Tetrahedron 2008, 64, 6494.
(c) Iseki, K.; Kuroki, Y.; Asada, D.; Takahashi, M.; Kishimoto, S.;
Kobayashi, Y. Tetrahedron 1997, 53, 10271. (d) Iseki, K.; Kuroki, Y.;
Asada, D.; Kobayashi, Y. Tetrahedron Lett. 1997, 38, 1447.
(e) Imashiro, R.; Kuroda, T. J. Org. Chem. 2003, 68, 974. (f) Kuroki,
Y.; Asada, D.; Iseki, K. Tetrahedron Lett. 2000, 41, 9853. (g) Blanc, D.;
In conclusion, highly enantiomerically enriched α,α-dichloro
or α,α-difluoro β-hydroxy esters and β-hydroxy amides can be
prepared through ruthenium-catalyzed asymmetric transfer
hydrogenation (ATH) of the corresponding ketones under
mild conditions. The use of commercially available precatalyst
[RuCl(p-cymene)(R,R)-TsDPEN] (S/C = 100−200) in the
presence of formic acid/triethylamine (5:2) as the hydrogen
source allowed the efficient reduction of a wide range of
nonaromatic α,α-dihalogeno β-keto esters in good to high
yields (up to 99% yield) and with excellent enantioselectivities
(up to >99% ee), whereas aromatic derivatives led to fair ee
values. The reaction was tolerant of various esters, as well as
being applicable to amides. Moreover, the ATH was efficiently
performed on gram-scale with compound 1a, demonstrating
the usefulness of this method.
̂
Ratovelomanana-Vidal, V.; Gillet, J.-P.; Genet, J.-P. J. Organomet.
Chem. 2000, 603, 128. (h) Mochizuki, N.; Sugai, T.; Ohta, H. Biosci.,
Biotechnol., Biochem. 1994, 58, 1666. (i) Ema, T.; Kadoya, T.; Akihara,
K.; Sakai, T. J. Mol. Catal. B: Enzym. 2010, 66, 198.
ASSOCIATED CONTENT
* Supporting Information
́
́
■
(5) (a) Echeverria, P.-G.; Cornil, J.; Ferard, C.; Guerinot, A.; Cossy,
J.; Phansavath, P.; Ratovelomanana-Vidal, V. RSC Adv. 2015, 5,
56815. (b) Monnereau, L.; Cartigny, D.; Scalone, M.; Ayad, T.;
Ratovelomanana-Vidal, V. Chem.Eur. J. 2015, 21, 11799. (c) Perez,
M.; Echeverria, P.-G.; Martinez-Arripe, E.; Ez Zoubir, M.; Touati, R.;
Zhang, Z.; Genet, J.-P.; Phansavath, P.; Ayad, T.; Ratovelomanana-
Vidal, V. Eur. J. Org. Chem. 2015, 2015, 5949. (d) Ayad, T.;
Phansavath, P.; Ratovelomanana-Vidal, V. Chem. Rec. 2016, 16, 2754.
S
The Supporting Information is available free of charge on the
Experimental procedures, compound characterization
data, NMR spectra and HPLC or SCF data for all new
́
(e) Zheng, L.-S.; Ferard, C.; Phansavath, P.; Ratovelomanana-Vidal,
V. Chem. Commun. 2018, 54, 283. (f) Zheng, L.-S.; Phansavath, P.;
Ratovelomanana-Vidal, V. Org. Chem. Front. 2018, 5, 1366.
Accession Codes
(6) (a) Noyori, R.; Hashiguchi, S. Acc. Chem. Res. 1997, 30, 97.
(b) Palmer, M. J.; Wills, M. Tetrahedron: Asymmetry 1999, 10, 2045.
(c) Everaere, K.; Mortreux, A.; Carpentier, J.-F. Adv. Synth. Catal.
2003, 345, 67. (d) Gladiali, S.; Alberico, E. Chem. Soc. Rev. 2006, 35,
CCDC 1850872 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
̈
226. (e) Samec, J. S. M.; Backvall, J.-E.; Andersson, P. G.; Brandt, P.
Chem. Soc. Rev. 2006, 35, 237. (f) Ikariya, T.; Blacker, A. J. Acc. Chem.
Res. 2007, 40, 1300. (g) Blacker, A. J. In Handbook of Homogeneous
Hydrogenation; de Vries, J. G., Elsevier, C. J., Eds.; Wiley−VCH:
́
Weinheim, 2007, 1215;. (h) Foubelo, F.; Najera, C.; Yus, M.
AUTHOR INFORMATION
Corresponding Authors
■
Tetrahedron: Asymmetry 2015, 26, 769. (i) Wang, D.; Astruc, D.
Chem. Rev. 2015, 115, 6621. (j) Echeverria, P.-G.; Ayad, T.;
Phansavath, P.; Ratovelomanana-Vidal, V. Synthesis 2016, 48, 2523.
(7) (a) Soleimannejad, J.; Sisson, A.; White, C. Inorg. Chim. Acta
savath).
nana-Vidal).
̌
2003, 352, 121. (b) Sterk, D.; Stephan, M. S.; Mohar, B. Tetrahedron
̌
Lett. 2004, 45, 535. (c) Sterk, D.; Stephan, M.; Mohar, B. Org. Lett.
2006, 8, 5935. (d) Mejía, E.; Aardoom, R.; Togni, A. Eur. J. Inorg.
Chem. 2012, 2012, 5021. (e) Cotman, A. E.; Cahard, D.; Mohar, B.
Angew. Chem., Int. Ed. 2016, 55, 5294. (f) Mohar, B.; Stephan, M.;
ORCID
D
Org. Lett. XXXX, XXX, XXX−XXX