Preparation of Enantioenriched Axially Chiral Anilides via [2+2+2] Cycloaddition of 1,6-Diynes with Trimethylsilylynamides

Ken Tanaka; Kenzo Takeishi

doi:10.1055/s-2007-983799

PSP

Preparation of Enantioenriched Axially Chiral Anilides via [2+2+2] Cycloaddition of 1,6-Diynes with Trimethylsilylynamides

Ken Tanaka*, Kenzo Takeishi
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan
Fax: +81(42)3887037; e-Mail: tanaka-k@cc.tuat.ac.jp;

Abstract

Alle Artikel dieser Rubrik

Abstract

The rhodium-catalyzed enantioselective [2+2+2] cycloaddition of 1,6-diynes with trimethylsilylynamides provides enantioenriched axially chiral anilides in poor to good yields with good to excellent enantioselectivity. Trimethylsilylynamides can be readily prepared in two steps starting from commercially available bis(trimethylsilyl)acetylene.

Key words

anilides - diynes - BINAP - rhodium - ynamides

Volltext

Referenzen

References

1 For the pioneering work on axially chiral N-substituted ortho-tert-butyl anilides, see: Curran DP. Qi H. Geib SJ. DeMello NC. J. Am. Chem. Soc. 1994, 116: 3131

For the synthesis of axially chiral anilides, see:

2a Kitagawa O. Izawa H. Sato K. Dobashi A. Taguchi T. Shiro M. J. Org. Chem. 1998, 63: 2634

2b Hughes AD. Price DA. Simpkins NS. J. Chem. Soc., Perkin Trans. 1 1999, 1295

2c Kondo K. Fujita H. Suzuki T. Murakami Y. Tetrahedron Lett. 1999, 40: 5577

2d Ates A. Curran DP. J. Am. Chem. Soc. 2001, 123: 5130

For the asymmetric synthesis of axially chiral anilides through enantiotopic deprotonation, see:

3a Hata T. Koide H. Taniguchi N. Uemura M. Org. Lett. 2000, 2: 1907

3b Koide H. Hata T. Yoshihara K. Kamikawa K. Uemura M. Tetrahedron 2004, 60: 4527

3c Bennett DJ. Pickering PL. Simpkins NS. Chem. Commun. 2004, 1392

4 For the stereoselective synthesis of axially chiral N-aryl indoles, see: Kamikawa K. Kinoshita S. Matsuzaka H. Uemura M. Org. Lett. 2006, 8: 1097

5a Kitagawa O. Kohriyama M. Taguchi T. J. Org. Chem. 2002, 67: 8682

5b Terauchi J. Curran DP. Tetrahedron: Asymmetry 2003, 14: 587

6a Kitagawa O. Takahashi M. Yoshikawa M. Taguchi T. J. Am. Chem. Soc. 2005, 127: 3676

6b Kitagawa O. Yoshikawa M. Tanabe H. Morita T. Takahashi M. Dobashi Y. Taguchi T. J. Am. Chem. Soc. 2006, 128: 12923

7 For our first report on the cationic rhodium(I)/modified-BINAP-catalyzed inter- and intramolecular [2+2+2] cycloadditions, see: Tanaka K. Shirasaka K. Org. Lett. 2003, 5: 4697

For the enantioselective synthesis of axially chiral biaryls, see:

8a Tanaka K. Nishida G. Wada A. Noguchi K. Angew. Chem. Int. Ed. 2004, 43: 6510

8b Tanaka K. Nishida G. Ogino M. Hirano M. Noguchi K. Org. Lett. 2005, 7: 3119

8c Tanaka K. Wada A. Noguchi K. Org. Lett. 2005, 7: 4737

8d Nishida G. Suzuki N. Noguchi K. Tanaka K. Org. Lett. 2006, 8: 3489

8e Tanaka K. Suda T. Noguchi K. Hirano M. J. Org. Chem. 2007, 72: 2243

8f Nishida G. Noguchi K. Hirano M. Tanaka K. Angew. Chem. Int. Ed. 2007, 46: 3951

8g Tanaka K. Otake Y. Wada A. Hirano M. Org. Lett. 2007, 9: 2203

9 For the enantioselective synthesis of axially chiral spiranes, see: Wada A. Noguchi K. Hirano M. Tanaka K. Org. Lett. 2007, 9: 1295

For the synthesis of cyclophanes, see:

10a Tanaka K. Toyoda K. Wada A. Shirasaka K. Hirano M. Chem. Eur. J. 2005, 11: 1145

10b Tanaka K. Sagae H. Toyoda K. Noguchi K. Eur. J. Org. Chem. 2006, 3575

For enantioselective synthesis of planar-chiral metacyclophanes, see:

10c Tanaka K. Sagae H. Toyoda K. Noguchi K. Hirano M. J. Am. Chem. Soc. 2007, 129: 1522

For the enantioselective construction of central chiralities, see:

11a Tanaka K. Wada A. Noguchi K. Org. Lett. 2006, 8: 907

11b Tanaka K. Suzuki N. Nishida G. Eur. J. Org. Chem. 2006, 3917

11c Tanaka K. Osaka T. Noguchi K. Hirano M. Org. Lett. 2007, 9: 1307

11d Tanaka K. Nishida G. Sagae H. Hirano M. Synlett 2007, 1426

12 Tanaka K. Takeishi K. Noguchi K. J. Am. Chem. Soc. 2006, 128: 4586

13 Stang PJ. In Modern Acetylene Chemistry Stang PJ. Diederich F. Wiley-VCH; Weinheim: 1995. p.67

14 Martinez-Esperón MF. Rodriguez D. Castedo L. Saá C. Org. Lett. 2005, 7: 2213

15 For a recent review of ynamides, see: Zificsak CA. Mulder JA. Hsung RP. Rameshkumar C. Wei L.-L. Tetrahedron 2001, 57: 7575

16 For the RhCl(PPh₃)₃-catalyzed [2+2+2] cycloadditions of ynamides leading to amide-substituted chiral biaryls, see: Tracey MR. Oppenheimer J. Hsung RP. J. Org. Chem. 2006, 71: 8629

For the RhCl(PPh₃) ₃-catalyzed [2+2+2] cycloadditions of ynamides for the synthesis of nitrogen heterocycles, see:

17a Witulski B. Stengel T. Angew. Chem. Int. Ed. 1999, 38: 2426

17b Witulski B. Alayrac C. Angew. Chem. Int. Ed. 2002, 41: 3281