Enantioselectivity Switch
in Direct Asymmetric Aminoxylation Catalyzed by Binaphthyl-Based
Chiral Secondary Amines

Taichi Kano; Akihiro Yamamoto; Fumitaka Shirozu; Keiji Maruoka

doi:10.1055/s-0029-1216635

SPECIALTOPIC

Enantioselectivity Switch in Direct Asymmetric Aminoxylation Catalyzed by Binaphthyl-Based Chiral Secondary Amines

Taichi Kano, Akihiro Yamamoto, Fumitaka Shirozu, Keiji Maruoka*
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan
Fax: +81(757)534041; e-Mail: maruoka@kuchem.kyoto-u.ac.jp;

Abstract

All articles of this category

Abstract

Binaphthyl-based amino acids (S)-1 and an aminosulfonamide (S)-2 were applied for direct asymmetric aminoxylation with nitrosobenzene. In the presence of either (S)-1 or (S)-2, the aminoxylation of aldehydes proceeded smoothly, and subsequent reduction with NaBH₄ gave 2-aminoxyl alcohols with good to excellent enantioselectivities. In each case, binaphthyl-based chiral amine catalysts (S)-1 and (S)-2, which have the identical axial chirality, gave opposite enantiomers as the major product. This method represents a rare example of the direct asymmetric aminoxylation by a non-proline type catalyst.

Key words

enamine catalysis - asymmetric aminoxylation - organocatalyst

Full Text

References

For reviews, see:

<A NAME="RC00209SS-1A">1a</A> Adam W. Krebs O. Chem. Rev. 2003, 103: 4131

<A NAME="RC00209SS-1B">1b</A> Merino P. Tejero T. Angew. Chem. Int. Ed. 2004, 43: 2995

<A NAME="RC00209SS-1C">1c</A> Janey JM. Angew. Chem. Int. Ed. 2005, 44: 4292

<A NAME="RC00209SS-1D">1d</A> Yamamoto H. Momiyama N. Chem. Commun. 2005, 3514

<A NAME="RC00209SS-1E">1e</A> Yamamoto Y. Yamamoto H. Eur. J. Org. Chem. 2006, 2031

<A NAME="RC00209SS-1F">1f</A> Yamamoto H. Kawasaki M. Bull. Chem. Soc. Jpn. 2007, 80: 595

<A NAME="RC00209SS-2">2</A> Momiyama N. Yamamoto H. J. Am. Chem. Soc. 2003, 125: 6038

Representative papers:

<A NAME="RC00209SS-3A">3a</A> Zhong G. Angew. Chem. Int. Ed. 2003, 42: 4247

<A NAME="RC00209SS-3B">3b</A> Brown SP. Brochu MP. Sinz CJ. MacMillan DWC. J. Am. Chem. Soc. 2003, 125: 10808

<A NAME="RC00209SS-3C">3c</A> Hayashi Y. Yamaguchi J. Hibino K. Shoji M. Tetrahedron Lett. 2003, 44: 8293

<A NAME="RC00209SS-3D">3d</A> Bøgevig A. Sundén H. Córdova A. Angew. Chem. Int. Ed. 2004, 43: 1109

<A NAME="RC00209SS-3E">3e</A> Hayashi Y. Yamaguchi J. Sumiya T. Shoji M. Angew. Chem. Int. Ed. 2004, 43: 1112

<A NAME="RC00209SS-3F">3f</A> Yamamoto Y. Momiyama N. Yamamoto H. J. Am. Chem. Soc. 2004, 126: 5962

<A NAME="RC00209SS-3G">3g</A> Momiyama N. Torii H. Saito S. Yamamoto H. Proc. Natl. Acad. Sci. U.S.A. 2004, 101: 5374

<A NAME="RC00209SS-3H">3h</A> Hayashi H. Yamaguchi J. Sumiya T. Hibino K. Shoji M. J. Org. Chem. 2004, 69: 5966

<A NAME="RC00209SS-3I">3i</A> Wang W. Wang J. Li H. Liao L. Tetrahedron Lett. 2004, 45: 7235

<A NAME="RC00209SS-3J">3j</A> Ramachary DB. Barbas CF. Org. Lett. 2005, 7: 1577

<A NAME="RC00209SS-3K">3k</A> Huang K. Huang Z.-Z. Li X.-L. J. Org. Chem. 2006, 71: 8320

<A NAME="RC00209SS-3L">3l</A> Font D. Bastero A. Sayalero S. Jimeno C. Pericàs MA. Org. Lett. 2007, 9: 1943

Representative papers on the asymmetric synthesis of natural products and chiral building blocks via organocatalytic aminoxylation:

<A NAME="RC00209SS-4A">4a</A> Enders D. Lenzen A. Müller M. Synthesis 2004, 1486

<A NAME="RC00209SS-4B">4b</A> Zhong G. Chem. Commun. 2004, 606

<A NAME="RC00209SS-4C">4c</A> Zhong G. Yu Y. Org. Lett. 2004, 6: 1637

<A NAME="RC00209SS-4D">4d</A> Kumarn S. Shaw DM. Longbottom DA. Ley SV. Org. Lett. 2005, 7: 4189

<A NAME="RC00209SS-4E">4e</A> Kumarn S. Shaw DM. Longbottom DA. Ley SV. Chem. Commun. 2006, 3211

<A NAME="RC00209SS-4F">4f</A> Kotkar SP. Sudalai A. Tetrahedron: Asymmetry 2006, 17: 1738

<A NAME="RC00209SS-4G">4g</A> Kim S.-G. Park T.-H. Kim BJ. Tetrahedron Lett. 2006, 47: 6369

<A NAME="RC00209SS-4H">4h</A> Kotkar SP. Sudalai A. Tetrahedron Lett. 2006, 47: 6813

<A NAME="RC00209SS-4I">4i</A> Talluri SK. Sudalai A. Tetrahedron 2007, 63: 9758

<A NAME="RC00209SS-5A">5a</A> Momiyama N. Yamamoto H. J. Am. Chem. Soc. 2005, 127: 1080

<A NAME="RC00209SS-5B">5b</A> Momiyama N. Yamamoto Y. Yamamoto H. J. Am. Chem. Soc. 2007, 129: 1190

<A NAME="RC00209SS-6">6</A> Momiyama N. Yamamoto H. J. Am. Chem. Soc. 2004, 126: 5360

<A NAME="RC00209SS-7A">7a</A> Guo H.-M. Cheng L. Cun L.-F. Gong L.-Z. Mi A.-Q. Jiang Y.-Z. Chem. Commun. 2006, 429

<A NAME="RC00209SS-7B">7b</A> Kano T. Ueda M. Takai J. Maruoka K. J. Am. Chem. Soc. 2006, 128: 6046

<A NAME="RC00209SS-7C">7c</A> Kim S.-G. Park T.-H. Tetrahedron Lett. 2006, 47: 9067

<A NAME="RC00209SS-7D">7d</A> Palomo C. Vera S. Velilla I. Mielgo A. Gómez-Bengoa E. Angew. Chem. Int. Ed. 2007, 46: 8054

<A NAME="RC00209SS-8">8</A> López-Cantarero CJ. Cid MB. Poulsen TB. Bella M. García Ruano JL. Jørgensen KA. J. Org. Chem. 2007, 72: 7062

<A NAME="RC00209SS-9A">9a</A> Yamamoto Y. Yamamoto H. J. Am. Chem. Soc. 2004, 126: 4128

<A NAME="RC00209SS-9B">9b</A> Yamamoto Y. Yamamoto H. Angew. Chem. Int. Ed. 2005, 44: 7082

<A NAME="RC00209SS-9C">9c</A> Jana CK. Studer A. Angew. Chem. Int. Ed. 2007, 46: 6542

<A NAME="RC00209SS-10A">10a</A> Kano T. Takai J. Tokuda O. Maruoka K. Angew. Chem. Int. Ed. 2005, 44: 3055

<A NAME="RC00209SS-10B">10b</A> Kano T. Tokuda O. Takai J. Maruoka K. Chem. Asian J. 2006, 1: 210

<A NAME="RC00209SS-11">11</A> Kano T. Yamaguchi Y. Maruoka K. Angew. Chem. Int. Ed. 2007, 46: 1738

<A NAME="RC00209SS-12A">12a</A> Kano T. Yamaguchi Y. Tokuda O. Maruoka K. J. Am. Chem. Soc. 2005, 127: 16408

<A NAME="RC00209SS-12B">12b</A> Kano T. Yamaguchi Y. Maruoka K. Angew. Chem. Int. Ed. 2009, 48: 1838

<A NAME="RC00209SS-13A">13a</A> Kano T. Yamamoto A. Mii H. Takai J. Shirakawa S. Maruoka K. Chem. Lett. 2008, 37: 250

<A NAME="RC00209SS-13B">13b</A> Kano T. Yamamoto A. Maruoka K. Tetrahedron Lett. 2008, 49: 5369

<A NAME="RC00209SS-14">14</A> Ooi T. Kameda M. Maruoka K. J. Am. Chem. Soc. 2003, 125: 5139

CCDC-710886 contains the supplementary crystallographic data of (S)-2˙HCl salt for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.