Organic Letters
Letter
Johnson, J. S.; Linghu, X.; Malinowski, J. T.; Nicewicz, D. A.;
Satterfield, A. D.; Schmitt, D. C.; Steward, K. M. J. Org. Chem. 2012,
77, 4503. (c) Smith, A. B., III; Wuest, W. M. Chem. Commun. 2008,
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Figure 1. Transition-state models.
́
(3) Selected reviews and examples: (a) Remond, E.; Martin, C.;
Martinez, J.; Cavelier, F. Chem. Rev. 2016, 116, 11654. (b) Henrion, S.;
Carboni, B.; Cossío, F. P.; Roisnel, T.; Villalgordo, J. M.; Carreaux, F.
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reacts with aldehyde to generate enamine A. Subsequently,
enamine A reacts with silyl glyoxylate through the transition
state B. The carbonyl group of silyl glyoxylate can be activated
by coordination to the proton of hydroxyl and carboxylic acid
via hydrogen bond. This interaction will be stronger in the
presence of an F atom13 on the ester group in the transition
state B. Therefore, the hydrogen bond is critical to this reaction.
In summary, a novel activation model for acylsilanes was
developed and realized by organocatalyzed direct aldol reaction
of silyl glyoxylates and aldehydes. This method enables efficient
synthesis of enantiopure α-hydroxysilanes in up to 99% ee and
>20:1 dr. There are several features in the reaction: (1)
commercially available cis-L-4-hydroxyproline is an ideal
organocatalyst for activating both aldehydes and acylsilanes;
(2) the hydrogen bond is critical to this reaction, and the
carbonyl group directly attached to silicon in acylsilanes could
be activated by the coordination effect of protons of hydroxyl
and carboxylic acid via hydrogen bond; (3) silyl glyoxylate 2i
with o-F on the benzene ring of benzyl ester was employed to
expand the reaction scope. Further studies of new reaction of
acylsilanes are currently underway in our laboratory.
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(c) Mohr, J. T.; Krout, M. R.; Stoltz, B. M. Nature 2008, 455, 323.
(d) Dondoni, A.; Massi, A. Angew. Chem., Int. Ed. 2008, 47, 4638.
(8) (a) Han, M.-Y.; Wang, H.-Z.; An, W.-K.; Jia, J.-Y.; Ma, B.-C.;
Zhang, Y.; Wang, W. Chem. - Eur. J. 2013, 19, 8078. (b) Han, M.-Y.;
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Adv. Synth. Catal. 2012, 354, 2635.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Full experimental details and characterization data for all
X-ray data for compound 5 (CIF)
AUTHOR INFORMATION
Corresponding Authors
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(9) Brook, A. G. J. Am. Chem. Soc. 1957, 79, 4373.
(10) Selected examples and reviews: (a) Itoh, T.; Ishikawa, H.;
Hayashi, Y. Org. Lett. 2009, 11, 3854. (b) Hayashi, Y.; Itoh, T.;
Aratake, S.; Ishikawa, H. Angew. Chem., Int. Ed. 2008, 47, 2082.
(c) Hayashi, Y.; Sumiya, T.; Takahashi, J.; Gotoh, H.; Urushima, T.;
Shoji, M. Angew. Chem., Int. Ed. 2006, 45, 958. (d) Notz, W.; Tanaka,
F.; Barbas, C. F., III Acc. Chem. Res. 2004, 37, 580. (e) List, B. Acc.
Chem. Res. 2004, 37, 548.
ORCID
Author Contributions
§M.-Y.H. and X.X. contributed equally to this work.
Notes
(11) (a) Hayashi, Y.; Shomura, H.; Xu, Q.; Lear, M. J.; Sato, I. Eur. J.
Org. Chem. 2015, 2015, 4316. (b) Kano, T.; Noishiki, A.; Sakamoto,
R.; Maruoka, K. Chem. Commun. 2011, 47, 10626. (c) Urushima, T.;
Yasui, Y.; Ishikawa, H.; Hayashi, Y. Org. Lett. 2010, 12, 2966.
(12) (a) Suzuki, I.; Esumi, N.; Yasuda, M. Asian J. Org. Chem. 2016,
5, 179. (b) Boyce, G. R.; Johnson, J. S. Angew. Chem., Int. Ed. 2010, 49,
8930. (c) Greszler, S. N.; Malinowski, J. T.; Johnson, J. S. J. Am. Chem.
Soc. 2010, 132, 17393. (d) Greszler, S. N.; Johnson, J. S. Angew. Chem.,
Int. Ed. 2009, 48, 3689.
The authors declare no competing financial interest.
Crystallographic data have been deposited with the Cambridge
Crystallographic Data Centre (CCDC 1536128).
ACKNOWLEDGMENTS
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We gratefully acknowledge the National Natural Science
Foundation of China (No. 21602073, 21572078) for financial
support.
(13) (a) Bulfield, D.; Huber, S. M. Chem. - Eur. J. 2016, 22, 14434.
(b) Kaplaneris, N.; Koutoulogenis, G.; Raftopoulou, M.; Kokotos, C.
G. J. Org. Chem. 2015, 80, 5464.
REFERENCES
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