Asymmetric Baylis-Hillman Reaction: An Enchanting Expedition

Abstract

The development of new strategies for realizing the asymmetric Baylis-Hillman reaction remains at the forefront of research into this important organic reaction. This review gives a comprehensive account of the work that has emanated from our group on the asymmetric Baylis-Hillman reaction. Herein, the use of homochiral electrophiles, Michael acceptors, and bases and double asymmetric induction protocols as tools for the asymmetric Baylis-Hillman reaction is discussed. The account also covers the application of such protocols in natural product synthesis.

1 Introduction

2 Asymmetric Baylis-Hillman Reaction: A Personal Account

2.1 Homochiral Electrophiles

2.1.1 Sugar-Derived Aldehydes

2.1.2 Chiral 2,3-Epoxy Aldehydes

2.2 Homochiral Michael Acceptors

2.2.1 TADDOL Acrylates

2.2.2 Sugar-Derived Acrylates

2.2.3 A Sugar-Derived Lactone

2.3 Homochiral Catalysts

2.3.1 N-Methylprolinol as the Chiral Catalyst

2.3.2 Other Chiral Catalysts

2.4 Double Asymmetric Induction

2.5 Applications

2.5.1 α-Methylene-β-hydroxylactones via an Intramolecular Baylis-Hillman Reaction

2.5.2 Synthesis of Syributins

2.5.3 Sequential Baylis-Hillman Reaction and Ring-Closing Metathesis as a Protocol for Sugar-Linked α,β-Unsaturated γ-Lactone Library Generation

2.5.4 Synthesis of Non-natural Higher-Carbon Sugars

3 Conclusion

Baylis-Hillman reaction - asymmetric synthesis - aldehydes - acrylates - natural products

References

<A NAME="RA49708ST-1">1</A> Morita K. Suzuki Z. Hirose H. Bull. Chem. Soc. Jpn.  1968,  41:  2815 

<A NAME="RA49708ST-2A">2a</A> Drewes SE. Roos GHP. Tetrahedron  1988,  44:  4653 

<A NAME="RA49708ST-2B">2b</A> Ciganek E. In Organic Reactions   Vol. 51:  Paquette LA. John Wiley & Sons; New York: 1997.  p.201 

<A NAME="RA49708ST-2C">2c</A> Langer P. Angew. Chem. Int. Ed.  2000,  39:  3049 

<A NAME="RA49708ST-2D">2d</A> Basavaiah D. Rao AJ. Satyanarayana T. Chem. Rev.  2003,  103:  811 

<A NAME="RA49708ST-2E">2e</A> Aggarwal VK. Fulford SY. Jones GCL. Angew. Chem. Int. Ed.  2005,  44:  1706 

<A NAME="RA49708ST-2F">2f</A> Price KE. Broadwater SJ. Walker BJ. McQuade DT. J. Org. Chem.  2005,  70:  3980 

<A NAME="RA49708ST-3A">3a</A> Shi M. Chen L.-H. Chem. Commun. (Cambridge)  2003,  1310 

<A NAME="RA49708ST-3B">3b</A> Matsui K. Takizawa S. Sasai H. J. Am. Chem. Soc.  2005,  127:  3680 

<A NAME="RA49708ST-3C">3c</A> Wang J. Li H. Yu X. Zu L. Wang W. Org. Lett.  2005,  7:  4293 

<A NAME="RA49708ST-3D">3d</A> Yang K.-S. Lee W.-D. Pan J.-F. Chen K. J. Org. Chem.  2003,  68:  915 

<A NAME="RA49708ST-3E">3e</A> McDougal NT. Schaus SE. J. Am. Chem. Soc.  2003,  125:  12094 

<A NAME="RA49708ST-3F">3f</A> Raheem IT. Jacobsen EN. Adv. Synth. Catal.  2005,  347:  1701 

<A NAME="RA49708ST-3G">3g</A> Krishna PR. Sharma GVM. Mini-Rev. Org. Chem.  2006,  3:  137 

<A NAME="RA49708ST-3H">3h</A> Shi M. Xu Y.-M. Angew. Chem. Int. Ed.  2002,  41:  4507 

<A NAME="RA49708ST-3I">3i</A> Shi M. Xu Y.-M. Shi Y.-L. Chem. Eur. J.  2005,  11:  1794 

<A NAME="RA49708ST-3J">3j</A> Shi M. Chen L.-H. Li C.-O. J. Am. Chem. Soc.  2005,  127:  3790 

<A NAME="RA49708ST-3K">3k</A> Iwabuchi Y. Nakatani M. Yokoyama N. Hatakeyama S. J. Am. Chem. Soc.  1999,  121:  102190 

<A NAME="RA49708ST-4A">4a</A> Sharma GVM. Hymavathi L. Radha Krishna P. Tetrahedron Lett.  1997,  38:  6929 

<A NAME="RA49708ST-4B">4b</A> Sharma GVM. Subash Chander A. Krishnudu K. Radha Krishna P. Tetrahedron Lett.  1997,  38:  9051 

<A NAME="RA49708ST-4C">4c</A> Sharma GVM. Goverdhan Reddy V. Radha Krishna P. Tetrahedron: Asymmetry  1999,  10:  3777 

<A NAME="RA49708ST-4D">4d</A> Sharma GVM. Srinivasa Reddy I. Goverdhan Reddy V. Rama Rao AV. Tetrahedron: Asymmetry  1999,  10:  229 

<A NAME="RA49708ST-5">5</A> Radha Krishna P. Kannan V. Sharma GVM. Ramana Rao MHV. Synlett  2003,  888 

<A NAME="RA49708ST-6">6</A> Yu C. Liu B. Hu L. J. Org. Chem.  2001,  66:  5413 

<A NAME="RA49708ST-7">7</A> Radha Krishna P. Manjuvani A. Kannan V. Tetrahedron: Asymmetry  2005,  16:  2691 

<A NAME="RA49708ST-8">8</A> Radha Krishna P. Manjuvani A. Kannan V. Sharma GVM. Tetrahedron Lett.  2004,  45:  1183 

<A NAME="RA49708ST-9">9</A> Radha Krishna P. Manjuvani A. Raja Sekhar E. ARKIVOC  2005,  (iii):  99 

<A NAME="RA49708ST-10">10</A> Roush WR. Adam M. Walts AE. Harris DJ. J. Am. Chem. Soc.  1986,  108:  3422 

<A NAME="RA49708ST-11">11</A> Katsuki T. Sharpless KB. J. Am. Chem. Soc.  1980,  102:  5974 

<A NAME="RA49708ST-12">12</A> Radha Krishna P. Krishna Rao L. Kannan V. Tetrahedron Lett.  2004,  45:  7847 

<A NAME="RA49708ST-13A">13a</A> Cornforth JW. Cornforth RH. Mathew KK. J. Am. Chem. Soc.  1959,  81:  112 

<A NAME="RA49708ST-13B">13b</A> Evans DA. Siska SJ. Cee VC. Angew. Chem. Int. Ed.  2003,  42:  1761 

<A NAME="RA49708ST-14A">14a</A> Mihelich ED. Tetrahedron Lett.  1979,  37:  1343 

<A NAME="RA49708ST-14B">14b</A> Martin VS. Woodard SS. Katsuki T. Yamada Y. Ikeda M. Sharpless KB. J. Am. Chem. Soc.  1981,  103:  6237 

<A NAME="RA49708ST-14C">14c</A> Roush WR. Brown RJ. J. Org. Chem.  1983,  48:  5093 

<A NAME="RA49708ST-14D">14d</A> Hwang G.-I. Chung J.-H. Lee WK. J. Org. Chem.  1996,  61:  6183 

<A NAME="RA49708ST-15A">15a</A> Toda F. Tanaka K. Tetrahedron Lett.  1988,  29:  551 

<A NAME="RA49708ST-15B">15b</A> Hafner A. Duthaler RO. Marti R. Ribs G. Streit RP. Schwarzenbach F. J. Am. Chem. Soc.  1992,  114:  2321 

<A NAME="RA49708ST-16">16</A>

Radha Krishna, P.; Sachwani, R. unpublished results.

<A NAME="RA49708ST-17">17</A> Radha Krishna P. Kannan V. Ilangovan A. Sharma GVM. Tetrahedron: Asymmetry  2001,  12:  829 

<A NAME="RA49708ST-18A">18a</A> Brzezinski LJ. Rafel S. Leahy JMT. Tetrahedron  1997,  53:  16423 

<A NAME="RA49708ST-18B">18b</A> Kunz H. Ruck K. Angew. Chem. Int. Ed.  1993,  32:  336 

<A NAME="RA49708ST-19">19</A> Radha Krishna P. Raja Sekhar E. Kannan V. Tetrahedron Lett.  2003,  44:  4973 

<A NAME="RA49708ST-20">20</A> Radha Krishna P. Srinivas Reddy P. Narsingam M. Sateesh B. Narahari Sastry G. Synlett  2006,  595 

<A NAME="RA49708ST-21">21</A> Yoon TP. Jacobsen EN. Science  2003,  299:  1691 

<A NAME="RA49708ST-22">22</A> Radha Krishna P. Kannan V. Narasimha Reddy PV. Adv. Synth. Catal.  2004,  346:  603 

<A NAME="RA49708ST-23">23</A>

Radha Krishna, P.; Sachwani, R. unpublished results.

<A NAME="RA49708ST-24">24</A> Masamune S. Choy W. Petersen JS. Lawrence RS. Angew. Chem. Int. Ed. Engl.  1985,  24:  1 

<A NAME="RA49708ST-25">25</A>

Radha Krishna, P.; Sachwani, R. unpublished results.

<A NAME="RA49708ST-26">26</A> Radha Krishna P. Sachwani R. Kannan V. Chem. Commun.  2004,  2580 

<A NAME="RA49708ST-27">27</A> Radha Krishna P. Kannan V. Sharma GVM. J. Org. Chem.  2004,  69:  6467 

<A NAME="RA49708ST-28">28</A> Radha Krishna P. Narsingam M. Kannan V. Tetrahedron Lett.  2004,  45:  4773 

<A NAME="RA49708ST-29">29</A> Radha Krishna P. Narsingam M. J. Comb. Chem.  2007,  9:  62 

<A NAME="RA49708ST-30">30</A> Radha Krishna P. Narasimha Reddy PV. Sreeshailam A. Uday Kiran M. Jagdeesh B. Tetrahedron Lett.  2007,  48:  6466