Abstract
A novel catalytic approach to asymmetric sulfinylation reaction based on the cinchona
alkaloid-sulfinyl chloride combination strategy is described.
Key words
asymmetric catalyst - sulfoxides - alkaloids - asymmetric synthesis - alcohols
References
<A NAME="RU12505ST-1A">1a </A>
Mikoajczk M.
Drabowicz J.
Kielbasinski P.
Chiral Sulfur Reagents
CRC Press;
Boca Raton:
1997.
<A NAME="RU12505ST-1B">1b </A>
Carreño MC.
Chem. Rev.
1995,
95:
1717
<A NAME="RU12505ST-1C">1c </A>
Toru T.
Nakamura S.
J. Synth. Org. Chem. Jpn.
2002,
60:
115
<A NAME="RU12505ST-1D">1d </A>
Khiar N.
Fernández I.
Alcudia A.
Alcudia F. In Advances in Sulfur Chemistry
2nd ed.:
Rayner CM.
JAI Press;
Stamford:
2000.
Chap. 3.
<A NAME="RU12505ST-1E">1e </A>
Fernández I.
Khiar N.
Chem. Rev.
2003,
103:
3651
<A NAME="RU12505ST-2A">2a </A>
Drabowicz J.
Lagedź S.
Mikoajczyk M.
Tetrahedron
1988,
44:
5243
<A NAME="RU12505ST-2B">2b </A>
Drabowicz J.
Legedź S.
Mikoajczyk M.
J. Chem. Soc., Chem. Commun.
1985,
1670
<A NAME="RU12505ST-2C">2c </A>
Mikoajczyk M.
Drabowicz J.
J. Chem. Soc., Chem. Commun.
1974,
547
<A NAME="RU12505ST-2D">2d </A>
Evans JW.
Fierman MB.
Miller SJ.
Ellman JA.
J. Am. Chem. Soc.
2004,
126:
8134
<A NAME="RU12505ST-2E">2e </A>
Nakamura S.
Tateyama M.
Sugimoto H.
Nakagawa M.
Watanabe Y.
Shibata N.
Toru T.
Chirality
2005,
17:
85
<A NAME="RU12505ST-3A">3a </A>
Phillips H.
J. Chem. Soc.
1925,
127:
2552
<A NAME="RU12505ST-3B">3b </A>
Fernández I.
Khiar N.
Llera JM.
Alcudia F.
J. Org. Chem.
1992,
57:
6789
<A NAME="RU12505ST-3C">3c </A>
Fernández I.
Khiar N.
Roca A.
Benabra A.
Alcudia A.
Espartero JL.
Alcudia F.
Tetrahedron Lett.
1999,
40:
2029
<A NAME="RU12505ST-3D">3d </A>
Khiar N.
Araújo CS.
Alcudia F.
Fernández I.
J. Org. Chem.
2002,
67:
345
<A NAME="RU12505ST-3E">3e </A>
Alayrac C.
Nowaczyk S.
Lemarié M.
Metzner P.
Synthesis
1999,
669
<A NAME="RU12505ST-3F">3f </A>
Whitesell JK.
Wong MS.
J. Org. Chem.
1991,
56:
4552
<A NAME="RU12505ST-3G">3g </A>
Whitesell JK.
Wong MS.
J. Org. Chem.
1994,
59:
597
<A NAME="RU12505ST-3H">3h </A>
Mase N.
Watanabe Y.
Ueno Y.
Toru T.
J. Org. Chem.
1997,
62:
7794
<A NAME="RU12505ST-3I">3i </A>
Watanabe Y.
Mase N.
Tateyama M.
Toru T.
Tetrahedron: Asymmetry
1999,
10:
737
<A NAME="RU12505ST-3J">3j </A>
Khiar N.
Alcudia F.
Espartero J.-L.
Rodríguez L.
Fernández I.
J. Am. Chem. Soc.
2000,
122:
7598
<A NAME="RU12505ST-3K">3k </A>
Lu BZ.
Jin F.
Zhang Y.
Wu X.
Wald SA.
Senanayake CH.
Org. Lett.
2005,
7:
1465
<A NAME="RU12505ST-4">4 </A>
Shibata N.
Matunaga M.
Nakagawa M.
Fukuzumi T.
Nakamura S.
Toru T.
J. Am. Chem. Soc.
2005,
127:
1374
<A NAME="RU12505ST-5A">5a </A>
Shibata N.
Suzuki E.
Takeuchi Y.
J. Am. Chem. Soc.
2000,
122:
10728
<A NAME="RU12505ST-5B">5b </A>
Shibata N.
Suzuki E.
Asahi T.
Shiro M.
J. Am. Chem. Soc.
2001,
123:
7001
<A NAME="RU12505ST-5C">5c </A>
Shibata N.
Ishimaru T.
Suzuki E.
Kirk KL.
J. Org. Chem.
2003,
68:
2494
<A NAME="RU12505ST-5D">5d </A>
Shibata N.
Ishimaru T.
Nakamura S.
Toru T.
Synlett
2004,
2509
<A NAME="RU12505ST-6">6 </A>
Typical Experimental Procedure.
A solution of 9-fluorenol (25 mg, 0.13 mmol) in toluene (1 mL) was slowly added to
a solution of 1 (0.025 mL, 0.20 mmol) and QDN (6.4 mg, 0.013 mmol) in toluene (2.0 mL) at -40 °C
under nitrogen atmosphere. To this solution was then added a solution of proton sponge
(72 mg, 0.34 mmol) in toluene (1 mL). After stirring at -40 °C for 36 h, the reaction
was quenched with 1 N NaOH solution (5 mL). The mixture was extracted with CH2 Cl2 (3 × 5 mL). The combined organic layer was dried over anhyd Na2 SO4 . The solution was evaporated under reduced pressure to give crude sulfinate, which
was purified by column chromatography (silica 25 g, EtOAc-hexane = 1:9) to give 3b (54 mg, 90%, 94% ee).
<A NAME="RU12505ST-7">7 </A> Just before the submission of the manuscript, a catalytic enantioselective sulfinyl
transfer using cinchona alkaloid catalysts was reported. See:
Peltier HM.
Evans JW.
Ellman JA.
Org. Lett.
2005,
7:
1733
<A NAME="RU12505ST-8">8 </A>
The catalytic enantioselective sulfinylation of alcohols using arenesulfinyl chlorides
instead of alkanesulfinyl chlorides was attempted; however, the enantioselectivities
of the arenesulfinates obtained were very low.