ORGANIC
LETTERS
2013
Vol. 15, No. 22
5658–5661
Asymmetric Oxidation Catalysis by a
Porphyrin-Inspired Manganese Complex:
Highly Enantioselective Sulfoxidation with
a Wide Substrate Scope
Wen Dai,†,‡,§ Jun Li,†,‡ Bo Chen,†,‡,§ Guosong Li,†,‡ Ying Lv,†,‡ Lianyue Wang,†,‡ and
Shuang Gao*,†,‡
Dalian Institute of Chemical Physics, the Chinese Academy of Sciences, Dalian, 116023,
People’s Republic of China, Dalian National Laboratory for Clean Energy,
People’s Republic of China, and University of Chinese Academy of Sciences,
Beijing 100049, People’s Republic of China
Received September 10, 2013
ABSTRACT
The first genuinely promising porphyrin-inspired manganese-catalyzed asymmetric sulfoxidation method using hydrogen peroxide has been successfully
developed, allowing for rapidly oxidizing (0.5À1.0 h) a wide variety of sulfides in high yields with excellent enantioselectivities (up to >99% ee).
Optically pure sulfoxides are extremely useful versatile
building blocks and chiral auxiliaries in organic synthesis.1
They have also been extensively applied in constituting many
bioactive compounds, including several marketed pharma-
ceuticals such as modafinil, sulindac, and esomeprazole.2
During the past few decades, intense effort has been devoted
to the development of various synthetic methods toward
enantioenriched sulfoxides.3 Among the available ap-
proaches developed, it is widely appreciated that the asym-
metric sulfoxidation is the most powerful and reliable route.
Since the initial breakthrough achieved in asymmetric sulfide
oxidation using modified Sharpless epoxidation catalysts by
Kagan in 1984,4 other catalytic systems based on titanium,5
vanadium,6 iron,7 aluminum,8 and copper9 have also been
developed; a high level enantioselectivity for certain classes of
sulfides such as simple aryl alkyl sulfides has been achieved.
(4) Pitchen, P.; Dunach, E.; Deshmukh, M.; Kagan, H. J. Am. Chem.
Soc. 1984, 106, 8188.
(5) For titanium-catalyzed oxidation of sulfides, see: (a) Komatsu,
N.; Nishibayashi, Y.; Sugita, T.; Uemura, S. Tetrahedron Lett. 1992, 33,
5391. (b) Di Furia, F.; Modena, G.; Seraglia, R. Synthesis 1984, 1984,
325. (c) Donnoli, M. I.; Superchi, S.; Rosini, C. J. Org. Chem. 1998, 63,
9392. (d) Yamanoi, Y.; Imamoto, T. J. Org. Chem. 1997, 62, 8560. (e)
Saito, B.; Katsuki, T. Tetrahedron Lett. 2001, 42, 3873. (f) Tanaka, T.;
Saito, B.; Katsuki, T. Tetrahedron Lett. 2002, 43, 3259.
(6) For vanadium-catalyzed oxidation of sulfides, see: (a) Bolm, C.;
Bienewald, F. Angew. Chem., Int. Ed. Engl. 1996, 34, 2640. (b) Vetter, A. H.;
Berkessel, A. Tetrahedron Lett. 1998, 39, 1741. (c) Pelotier, B.; Anson,
M. S.; Campbell, I. B.; Macdonald, S. J.; Priem, G.; Jackson, R. F. Synlett
2002, 2002, 1055. (d) Drago, C.; Caggiano, L.; Jackson, R. F. Angew.
Chem., Int. Ed. 2005, 44, 7221. (e) Hinch, M.; Jacques, O.; Drago, C.;
Caggiano, L.; Jackson, R. F.; Dexter, C.; Anson, M. S.; Macdonald, S. J.
J. Mol. Catal. A: Chem. 2006, 251, 123. (f) Mohammadpoor-Baltork, I.;
Hill, M.; Caggiano, L.; Jackson, R. F. Synlett 2006, 2006, 3540.
(7) For iron-catalyzed oxidation of sulfides, see: (a) Legros, J.; Bolm,
C. Angew. Chem., Int. Ed. 2003, 42, 5487. (b) Legros, J.; Bolm, C.
Chem.;Eur. J. 2005, 11, 1086. (c) Egami, H.; Katsuki, T. J. Am. Chem.
Soc. 2007, 129, 8940. (d) Bryliakov, K. P.; Talsi, E. P. Chem.;Eur. J.
2007, 13, 8045.
† Dalian Institute of Chemical Physics.
‡ Dalian National Laboratory for Clean Energy.
§ University of Chinese Academy of Sciences.
~
ꢀ
(1) (a) Carreno, M. C.; Hernandez-Torres, G.; Ribagorda, M.;
Urbano, A. Chem. Commun. 2009, 6129. (b) Mellah, M.; Voituriez,
A.; Schulz, E. Chem. Rev. 2007, 107, 5133. (c) Kobayashi, S.; Ogawa, C.;
Konishi, H.; Sugiura, M. J. Am. Chem. Soc. 2003, 125, 6610.
(2) (a) Bentley, R. Chem. Soc. Rev. 2005, 34, 609. (b) Legros, J.; Dehli,
ꢁ
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J. R.; Bolm, C. Adv. Synth. Catal. 2005, 347, 19. (c) Liao, S.; Coric, I.;
ꢀ
Wang, Q.; List, B. J. Am. Chem. Soc. 2012, 134, 10765. (d) Fernandez, I.;
Khiar, N. Chem. Rev. 2003, 103, 3651.
(3) (a) O’Mahony, G. E.; Ford, A.; Maguire, A. R. J. Sulfur Chem.
2013, 34, 301. (b) Stingl, K. A.; Tsogoeva, S. B. Tetrahedron: Asymmetry
2010, 21, 1055. (c) Dembitsky, V. M. Tetrahedron 2003, 59, 4701.
r
10.1021/ol402612x
Published on Web 10/24/2013
2013 American Chemical Society