Organic Letters
Letter
(e) Harikrishna, M.; Rama Mohan, H.; Dubey, P. K.; Shankar, M.;
Subbaraju, G. V. Synth. Commun. 2012, 42, 1288. (f) Dams, I.;
shorter and more efficient syntheses of the lower side chains.
Furthermore, as a result of using the crystalline lactone 10 as an
intermediate, these compounds were prepared with very high
enantiopurity. The significantly reduced step count should lead
to lower costs in the production of these important drugs, thus
enabling more people to have access to these effective medicines.
Chodyn
́
ski, M.; Krupa, M.; Pietraszek, A.; Zezula, M.; Cmoch, P.;
Kosinska, M.; Kutner, A. Chirality 2013, 25, 170.
́
(9) Coulthard, G.; Erb, W.; Aggarwal, V. K. Nature 2012, 489, 278.
(10) Hayashi, Y.; Umemiya, S. Angew. Chem., Int. Ed. 2013, 52, 3450.
(11) Aggarwal, V. K.; Coulthard, G.; Erb, W. PCT Int. Appl. (2013)
WO 2013/186550 A1.
ASSOCIATED CONTENT
* Supporting Information
(12) (a) Hoover, J. M.; Stahl, S. S. J. Am. Chem. Soc. 2011, 133, 16901.
(b) Hoover, J. M.; Ryland, B. L.; Stahl, S. S. J. Am. Chem. Soc. 2013, 135,
2357.
(13) (a) Kim, I. S.; Ngai, M.-Y.; Krische, M. J. J. Am. Chem. Soc. 2008,
130, 14891. (b) Hassan, A.; Lu, Y.; Krische, M. J. Org. Lett. 2009, 11,
3112.
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S
Experimental procedures, characterization data, and NMR
spectra for all new compounds. This material is available free
(14) (a) Victor Paul Raj, I.; Sudalai, A. Tetrahedron Lett. 2008, 49, 2646.
AUTHOR INFORMATION
Corresponding Author
́
(b) Fernandez, E.; Pietruszka, J.; Frey, W. J. Org. Chem. 2010, 75, 5580.
(c) Denmark, S. E.; Heemstra, J. R., Jr. J. Am. Chem. Soc. 2005, 128, 1038.
(d) Denmark, S. E.; Wilson, T. W. Angew. Chem., Int. Ed. 2012, 51, 3236.
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Notes
(e) Nunez, M. T.; Martín, V. S. J. Org. Chem. 1990, 55, 1928. (f) Peng,
̃
F.; Hall, D. G. Tetrahedron Lett. 2007, 48, 3305.
(15) (a) Bovall, D.; Lop
Org. Lett. 2000, 2, 4233. (b) Frantz, D. E.; Fassler, R.; Carreira, E. M. J.
́
ez, F.; Sasaki, H.; Frantz, D.; Carreira, E. M.
The authors declare no competing financial interest.
̈
Am. Chem. Soc. 2000, 122, 1806. Carreira reported that addition of the
acetylide anion to the primary aliphatic aldehyde, hexanal, only gave 51%
ee using 1.2 equiv of NME and 1.1 equiv of Zn(OTf)2 but 98% ee using
2.1 equiv of NME and 2.0 equiv of Zn(OTf)2. As such we used the latter
conditions.
(16) For the original work on (noncatalytic) asymmetric addition of
acetylide anions to aldehydes and ketones, see: (a) Niwa, S.; Soai, K. J.
Chem. Soc., Perkin Trans. 1 1990, 937. (b) Ramos Tombo, G. M.; Didier,
E.; Loubinoux, B. Synlett 1990, 547. (c) Tan, L.; Chen, C.; Tillyer, R. D.;
Grabowski, E. J. J.; Reider, P. J. Angew. Chem., Int. Ed. 1999, 38, 711.
(d) Li, Z.; Upadhyay, V.; DeCamp, A. E.; DiMichele, L.; Reider, P. J.
Synthesis 1999, 1453. For the first application of the catalytic
methodology in total synthesis, see: (e) Hale, K. J.; Grabski, M.;
Manaviazar, S.; Maczka, M. Org. Lett. 2014, 16, 1164. (f) Hale, K. J.;
Hatakeyama, S.; Urabe, F.; Ishihara, J.; Manaviazar, S.; Grabski, M.;
Maczka, M. Org. Lett. 2014, 16, 3536.
ACKNOWLEDGMENTS
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We thank the EPSRC and the European Research Council (FP7/
2007-2013, ERC Grant No. GA 620237) for financial support.
N.S. thanks the Deutsche Forschungsgemeinschaft (DFG) and
the Marie Curie Fellowship program (EC FP7 623426) for
postdoctoral fellowships.
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