Hydroxymethylpyridine Catalysts for the Enantioselective Alkynylation of Aldehydes

Sabrina Liebehentschel; Ján Cvengroš; Axel Jacobi von Wangelin

doi:10.1055/s-2007-986630

LETTER

Hydroxymethylpyridine Catalysts for the Enantioselective Alkynylation of Aldehydes

Sabrina Liebehentschel, Ján Cvengroš, Axel Jacobi von Wangelin*
Department of Organic Chemistry, University of Cologne, Greinstr. 4, 50939 Köln, Germany
Fax: +49(221)4705057; e-Mail: axel.jacobi@uni-koeln.de;

Abstract

All articles of this category

Abstract

Chiral 2-hydroxymethylpyridines based on fenchol and menthol were evaluated as catalysts for the enantioselective addition of terminal alkynes to aldehydes. With one of the fenchol-based ligands, the operationally simple protocol gave propargylic alcohols with excellent yields and up to 85% ee for various aldehyde and alkyne derivatives.

Keywords

alkynes - propargylic alcohols - pyridines - asymmetric catalysis - zinc

Full Text

References

For reviews on alkyne additions to carbonyl compounds, see:

<A NAME="RG09207ST-1A">1a</A> Frantz DE. Fässler R. Tomooka CS. Carreira EM. Acc. Chem. Res. 2000, 33: 373

<A NAME="RG09207ST-1B">1b</A> Pu L. Tetrahedron 2003, 59: 9873

<A NAME="RG09207ST-1C">1c</A> Cozzi PG. Hilgraf R. Zimmermann N. Eur. J. Org. Chem. 2004, 4095

<A NAME="RG09207ST-1D">1d</A> Aschwanden PA. Carreira EM. In Acetylene Chemistry: Chemistry, Biology, and Material Science Diederich F. Stang PJ. Tykwinski RR. Wiley-VCH; Weinheim: 2005. p.101

<A NAME="RG09207ST-2A">2a</A> Modern Acetylene Chemistry Stang PJ. Diederich F. VCH; Weinheim: 1995.

<A NAME="RG09207ST-2B">2b</A> Marshall JA. Wang XJ. J. Org. Chem. 1992, 57: 1242

<A NAME="RG09207ST-2C">2c</A> Corey EJ. Cimprich KA. J. Am. Chem. Soc. 1994, 116: 3151

<A NAME="RG09207ST-2D">2d</A> Roush WR. Sciotti RJ. J. Am. Chem. Soc. 1994, 116: 6457

<A NAME="RG09207ST-2E">2e</A> Myers AG. Zheng B. J. Am. Chem. Soc. 1996, 118: 4492

<A NAME="RG09207ST-2F">2f</A> Trost BM. Krische MJ. J. Am. Chem. Soc. 1999, 121: 6131

For reviews on organozinc chemistry, see:

<A NAME="RG09207ST-3A">3a</A> Knochel P. Calaza MI. Hupe E. In Metal-Catalyzed Cross-Coupling Reactions 2nd ed.: de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004. p.619

<A NAME="RG09207ST-3B">3b</A> Knochel P. Millot N. Rodriguez A. Tucker CE. Org. React. 2001, 58: 417

<A NAME="RG09207ST-3C">3c</A> Jacobi von Wangelin A. Frederiksen MU. In Transition Metals for Organic Synthesis 2nd ed.: Beller M. Bolm C. Wiley-VCH; Weinheim: 2004. p.519

<A NAME="RG09207ST-4">4</A> Kamble MJ. Singh VK. Tetrahedron Lett. 2003, 44: 5347

<A NAME="RG09207ST-5A">5a</A> Frantz DE. Fässler R. Carreira EM. J. Am. Chem. Soc. 2000, 122: 1806

<A NAME="RG09207ST-5B">5b</A> Anand NK. Carreira EM. J. Am. Chem. Soc. 2001, 123: 9687

<A NAME="RG09207ST-6A">6a</A> Watts CC. Thoniyot P. Hirayama LC. Romano T. Singaram B. Tetrahedron: Asymmetry 2005, 16: 1829

<A NAME="RG09207ST-6B">6b</A> Yamashita M. Yamadam K. Omioka K. Adv. Synth. Catal. 2005, 347: 1649

<A NAME="RG09207ST-6C">6c</A> Emmerson DPG. Hems WP. Davis BJ. Org. Lett. 2006, 8: 207

<A NAME="RG09207ST-7">7</A> Li M. Zhu X.-Z. Yuan K. Cao B.-X. Hou X.-L. Tetrahedron: Asymmetry 2004, 15: 219

<A NAME="RG09207ST-8">8</A> Dahmen S. Org. Lett. 2004, 6: 2113

<A NAME="RG09207ST-9A">9a</A> Braga AL. Appelt HR. Silveria CC. Wessjohann LA. Schneider PH. Tetrahedron 2002, 58: 10413

<A NAME="RG09207ST-9B">9b</A> Kang Y. Wang R. Liu L. Da C. Yan W. Xu Z. Tetrahedron Lett. 2005, 46: 863

<A NAME="RG09207ST-10">10</A> Han Z. Wang R. Zhou Y. Liu L. Eur. J. Org. Chem. 2005, 934

<A NAME="RG09207ST-11A">11a</A> Fang T. Du D.-M. Lu SF. Xu J. Org. Lett. 2005, 7: 2081

<A NAME="RG09207ST-11B">11b</A> Li X. Lu G. Kwok WH. Chan ASC. J. Am. Chem. Soc. 2002, 124: 12636

<A NAME="RG09207ST-12">12</A> Blay G. Fernández I. Marco-Aleixandre A. Pedro JR. J. Org. Chem. 2006, 71: 6674

<A NAME="RG09207ST-13A">13a</A> Wang Q. Chen S.-Y. Yua X.-Q. Pu L. Tetrahedron 2007, 63: 4422

<A NAME="RG09207ST-13B">13b</A> Lu G. Li X. Chen G. Chan WL. Chan ASC. Tetrahedron: Asymmetry 2003, 14: 449

<A NAME="RG09207ST-14A">14a</A> Trost BM. J. Am. Chem. Soc. 2000, 122: 12003

<A NAME="RG09207ST-14B">14b</A> Trost BM. Ito H. Silcoff ER. J. Am. Chem. Soc. 2001, 123: 3367

<A NAME="RG09207ST-14C">14c</A> Trost BM. Mino T. J. Am. Chem. Soc. 2003, 125: 2410

<A NAME="RG09207ST-14D">14d</A> Trost BM. Fettes A. Shireman BT. J. Am. Chem. Soc. 2004, 126: 2660

<A NAME="RG09207ST-14E">14e</A> Trost BM. Shin S. Sclafani JA. J. Am. Chem. Soc. 2005, 127: 8602

<A NAME="RG09207ST-14F">14f</A> Trost BM. Yeh VSC. Angew. Chem. Int. Ed. 2002, 41: 861 ; Angew. Chem. 2002, 114, 889

<A NAME="RG09207ST-14G">14g</A> Trost BM. Weiss AH. Jacobi von Wangelin A. J. Am. Chem. Soc. 2006, 128: 8

<A NAME="RG09207ST-15A">15a</A> Bolm C. Schlingloff G. Harms K. Chem. Ber. 1992, 125: 1191

<A NAME="RG09207ST-15B">15b</A> Kwong H.-L. Lee W.-S. Tetrahedron: Asymmetry 1999, 10: 3791

<A NAME="RG09207ST-15C">15c</A> Bolm C. Ewald M. Zehnder M. Neuburger MA. Chem. Ber. 1992, 125: 453

<A NAME="RG09207ST-15D">15d</A> For the preparation of related chiral hydroxymethyl-pyridines, see: Bolm C. Ewald M. Felder M. Schlingloff G. Chem. Ber. 1992, 125: 1169

<A NAME="RG09207ST-16">16</A> For precedent reference regarding SAR calculations of chiral fenchone-based organozinc catalysts, see: Goldfuss B. Steigelmann M. J. Mol. Model. 2000, 6: 166

For precedents on the asymmetric addition to aldehydes using chiral fenchone-based ligands, see:

<A NAME="RG09207ST-17A">17a</A> Goldfuss B. Steigelmann M. Khan SI. Houk KN. J. Org. Chem. 2000, 65: 77

<A NAME="RG09207ST-17B">17b</A> Genov M. Kostova K. Dimitrov V. Tetrahedron: Asymmetry 1997, 8: 1869

<A NAME="RG09207ST-18">18</A> Herrmann WA. Haider JJ. Fridgen J. Lobmaier GM. Spiegler M. J. Organomet. Chem. 2000, 603: 69

<A NAME="RG09207ST-19A">19a</A> El Sheikh S. Schmalz H.-G. Curr. Opin. Drug Discovery Dev. 2004, 7: 882

<A NAME="RG09207ST-19B">19b</A> Elmas S. Schmalz H.-G. Diploma Thesis Universität zu Köln; Germany: 2005.

Goto, S.; Velder, J.; El Sheikh, S.; Sakamoto, Y.; Mitani, M.; Elmas, S.; Adler, A.; Becker, A.; Neudörfl, J.-M.; Schmalz, H.-G.; manuscript in preparation.

<A NAME="RG09207ST-20">20</A> For a concise review on chiral camphor-based pyridines, see: Chelucci G. Chem. Soc. Rev. 2006, 35: 1230

<A NAME="RG09207ST-21">21</A> Cozzi and coworkers reported on the ligand-free preformation of alkynylzinc species within 30 min: Cozzi PG. Rudolph J. Bolm C. Norrby P.-O. Tomasini C. J. Org. Chem. 2005, 70: 5733

<A NAME="RG09207ST-22">22</A> Noyori R. Kitamura M. Angew. Chem. Int. Ed. 2002, 30: 49 ; Angew. Chem. 1991, 103, 34

<A NAME="RG09207ST-23">23</A> Buckle DR. Fenwick AE. J. Chem. Soc., Perkin Trans. 1 1989, 3: 477