Journal of the American Chemical Society
Article
(17) Pilkington, C. J.; Zanotti-Gerosa, A. Org. Lett. 2003, 5, 1273−
1275.
(18) Pelotier, B.; Anson, M. S.; Campbell, I. B.; Macdonald, S. J. F.;
Priem, G.; Jackson, R. F. W. Synlett 2002, 1055−1060.
(19) Substrate (S)-1b could be stored neat for several months in the
freezer without significant racemization.
(20) For other examples of asymmetric sulfide oxidation, see:
(a) Pitchen, P.; Dunach, E.; Deshmukh, M. N.; Kagan, H. B. J. Am.
Chem. Soc. 1984, 106, 8188−8193. (b) Dai, W.; Li, J.; Chen, B.; Li, G.;
Lv, Y.; Wang, L.; Gao, S. Org. Lett. 2013, 15, 5658−5661 and
references therein.
(21) Overman, L. E. Angew. Chem., Int. Ed. Engl. 1984, 23, 579−586.
(22) Schenck, T. G.; Bosnich, B. J. Am. Chem. Soc. 1985, 107, 2058−
2066.
developing new catalysts and strategies for promoting allylic
sulfoxide racemization.
ASSOCIATED CONTENT
* Supporting Information
■
S
Full synthetic and characterization details, energies, and
optimized geometries of all calculated species. This material
AUTHOR INFORMATION
Corresponding Authors
■
(23) Lee, E. E.; Batey, R. A. J. Am. Chem. Soc. 2005, 127, 14887−
14893.
Author Contributions
∥These authors contributed equally.
(24) Bao, H.; Qi, X.; Tambar, U. K. J. Am. Chem. Soc. 2011, 133,
1206−1208.
(25) A small amount of dichloromethane was used in the solvent
mixture in order to ensure solubility of the catalyst throughout the
experiment.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
(26) Reist, M.; Testa, B.; Carrupt, P.-A.; Jung, M.; Schurig, V.
■
Chirality 1995, 7, 396−400.
(27) Ikariya, T.; Ishikawa, Y.; Hirai, K.; Yoshikawa, S. Chem. Lett.
1982, 1815−1818.
K.N.H. thanks the National Science Foundation (CHE-
0548209) and V.M.D. thanks the National Institute of Health
(GM105938) and Eli Lilly for financial support. P.K.D. is
grateful for an NSERC Vanier award and an NSERC Michael
Smith Foreign Study Supplement. K.G.M.K. is grateful for an
NSERC CGS-D award. We thank Dr. Peng Liu for helpful
discussions. Computations were performed on the IDRE
Hoffman2 cluster at UCLA and the HPCVL cluster at Queen’s
University, Kingston.
(28) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci,
B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H.
P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.;
Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima,
T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.;
Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin,
K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.;
Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega,
N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.;
Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.;
Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.;
Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.;
REFERENCES
■
(1) Fernan
́
dez, I.; Khiar, N. Chem. Rev. 2003, 103, 3651−3706.
(2) For select examples of sulfoxides used as chiral auxiliaries, see:
(a) Adrio, J.; Carretero, J. C. J. Am. Chem. Soc. 1999, 121, 7411−7412.
(b) Maezaki, N.; Sakamoto, A.; Nagahashi, N.; Soejima, M.; Li, Y.-X.;
Imamura, T.; Kojima, N.; Ohishi, H.; Sakaguchi, K.; Iwata, C.; Tanaka,
̈
Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman,
J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09; Gaussian Inc.:
Wallingford, CT, 2010.
T. J. Org. Chem. 2000, 65, 3284−3291. (c) Carreno, M. C.; Des
̃
Mazery, R.; Urbano, A.; Colobert, F.; Solladie,
297−299.
́
G. Org. Lett. 2004, 6,
(29) Zhao, Y.; Truhlar, D. G. Theor. Chem. Acc. 2007, 120, 215−241.
(30) Jones-Hertzog, D. K.; Jorgensen, W. L. J. Am. Chem. Soc. 1995,
117, 9077−9078.
(31) Amaudrut, J.; Pasto, D. J.; Wiest, O. J. Org. Chem. 1998, 63,
6061−6064.
(32) Freeman, F.; Bathala, R. M.; Cavillo, J. E.; Huang, A. C.;
Jackson, T. K.; Lopez-Mercado, A. Z.; Phung, S.; Suh, J.; Valencia, D.
O. Int. J. Quantum Chem. 2006, 106, 2390−2397.
(33) Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B
2009, 113, 6378−6396.
(34) Faller, J. W.; Thomsen, M. E.; Mattina, M. J. J. Am. Chem. Soc.
1971, 93, 2642−2653.
(3) Chen, M. S.; Prabagaran, N.; Labenz, N. A.; White, M. C. J. Am.
Chem. Soc. 2005, 127, 6970−6971.
(4) Mariz, R.; Luan, X.; Gatti, M.; Linden, A.; Dorta, R. J. Am. Chem.
Soc. 2008, 130, 2172−2173.
(5) Burgi, J. J.; Mariz, R.; Gatti, M.; Drinkel, E.; Luan, X.;
̈
Blumentritt, S.; Linden, A.; Dorta, R. Angew. Chem., Int. Ed. 2009,
48, 2768−2771.
(6) Coulter, M. M.; Dornan, P. K.; Dong, V. M. J. Am. Chem. Soc.
2009, 131, 6932−6933.
(7) Rayner, D. R.; Miller, E. G.; Bickart, P.; Gordon, A. J.; Mislow, K.
J. Am. Chem. Soc. 1966, 88, 3138−3139.
(35) A Rh-catalyzed racemization pathway without allylic trans-
position could occur if reductive elimination occurred directly from
intermediate 9. This reductive elimination was found to have a barrier
of 19.5 kcal/mol.
(8) Bickart, P.; Carson, F. W.; Jacobus, J.; Miller, E. G.; Mislow, K. J.
Am. Chem. Soc. 1968, 90, 4869−4876.
(9) Tang, R.; Mislow, K. J. Am. Chem. Soc. 1970, 92, 2100−2104.
(10) Evans, D. A.; Andrews, G. C. Acc. Chem. Res. 1974, 7, 147−155.
(11) Akai, S.; Tanimoto, K.; Kanao, Y.; Egi, M.; Yamamoto, T.; Kita,
Y. Angew. Chem., Int. Ed. 2006, 45, 2592−2595.
(12) Akai, S.; Hanada, R.; Fujiwara, N.; Kita, Y.; Egi, M. Org. Lett.
2010, 12, 4900−4903.
(36) Consiglio, G.; Waymouth, R. M. Chem. Rev. 1989, 89, 257−276.
(37) Katayama, T.; Nitta, T. J. Chem. Eng. Data 1976, 21, 194−196.
̌
(38) Turecek, F. J. Phys. Chem. A 1998, 102, 4703−4713.
(39) The amount of sulfenate ester generated was found to be higher
using the low-pressure conditions. To explain this observation, we
note that allyl sulfenate ester 2 is a transient intermediate in the
racemization process and not observable by 1H NMR. Under
conditions where the racemization is fast relative to hydrogenation,
the ratio of allyl sulfenate ester 2 to sulfoxide 1 can be maintained at
thermodynamic equilibrium. This scenario is relevant for entry 7,
where high ee and 10% sulfenate was observed. However if the
racemization is slow relative to hydrogenation, then formation of allyl
(13) Levin, S.; Nani, R. R.; Reisman, S. E. J. Am. Chem. Soc. 2011,
133, 774−776.
(14) Zhou, Z. S.; Flohr, A.; Hilvert, D. J. Org. Chem. 1999, 64, 8334−
8341.
(15) Kleimark, J.; Prestat, G.; Poli, G.; Norrby, P.-O. Chem.Eur. J.
2011, 17, 13963−13965.
(16) Kitamura, M.; Tokunaga, M.; Noyori, R. J. Am. Chem. Soc. 1993,
115, 144−152.
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