Organic Letters
Letter
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requiring just 1 mol % of an ATH catalyst. Completion of the
formal total synthesis also provided a means to confirm the
absolute stereochemistry of 31 as R, through comparison of the
sign of optical rotation, and the HPLC data, to that previously
reported.13b
In conclusion, we have demonstrated that ATH can be used
effectively to reduce aryl/alkynyl ketones in high enantiomeric
excess and conversion, provided that the substrate satisfies certain
requirements which place them in a “window” of high
compatibility with the catalyst. The results demonstrate that the
low initial enantioselectivity on the simple unsubstituted
compound 7 can be improved and optimized through under-
standing of the factors governing stereocontrol.
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ASSOCIATED CONTENT
* Supporting Information
TheSupportingInformationisavailablefreeofchargeontheACS
■
S
Experimental procedures, NMR spectra, and HPLC and X-
Accession Codes
crystallographic data for this paper. These data can be obtained
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
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AUTHOR INFORMATION
Corresponding Authors
■
ORCID
(13) (a) Georgy, M.; Boucard, V.; Campagne, J.-M. J. Am. Chem. Soc.
2005, 127, 14180. (b) Leblanc, M.; Fagnou, K. Org. Lett. 2005, 7, 2849.
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E110. (b) Eagon, S.; DeLieto, C.; McDonald, W. J.; Haddenham, D.;
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(15)(a) Sasaki, H.;Boyall, D.;Carreira, E. M. Helv. Chim. Acta2001, 84,
Notes
The authors declare no competing financial interest.
964. (b) Frantz, D. E.; Fassler, R.; Carreira, E. M. J. Am. Chem. Soc. 2000,
̈
ACKNOWLEDGMENTS
122, 1806. (c) Anand, N. K.; Carreira, E. M. J. Am. Chem. Soc. 2001, 123,
9687. (d) El-Sayed, E.; Anand, N. K.; Carreira, E. M. Org. Lett. 2001, 3,
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B.; Li, Z.; Liu, F.; Wu, Y.; Shen, J.; Bian, Q.; Hou, S.; Wang, M. Molecules
2013, 18, 15422.
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Am. Chem. Soc. 2005, 127, 13760. (d) Corey, E. J.; Cimprich, K. A. J. Am.
Chem. Soc. 1994, 116, 3151.
■
V.K.V. acknowledges the PhD funding agency Department of
Science & Technology (DST) INSPIRE (SRF) as well as the
Newton Bhabha fund of the Royal Society and Warwick
University. EPSRC is thanked for a project grant (EP/
M006670/1) (R.C.K.). We thank Johnson Matthey Catalysts
for a gift of catalyst 2. Crystallographic data for 26 were collected
using instruments purchased through support from Advantage
West Midlands and the European Regional Development Fund.
Crystallographic data for 37 were collected using an instrument
funded by the ERC under the European Union’s Horizon 2020
research and innovation programme (Grant No. 637313).
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