Baylis-Hillman Reaction of Cyclic Enones with Arenecarbaldehydes and N-Arylidene-4-methylbenzenesulfonamides by Using NAP-MgO

Abstract

Baylis-Hillman reaction of cyclic enones with arene­carbaldehydes and N-arylidene-4-methylbenzenesulfonamides under mild conditions by using nanocrystalline MgO (NAP-MgO) afforded the Baylis-Hillman adducts in moderate to good yields with higher selectivity than the corresponding aldol products.

Baylis-Hillman reaction - cyclic enones - NAP-MgO - heterogeneous - solid base

References and Notes

<A NAME="RD00508ST-1A">1a</A> Mortia K. Suzuki Z. Hirose H. Bull. Chem. Soc. Jpn.  1968,  41:  2815 

<A NAME="RD00508ST-1B">1b</A> Basavaiah D. Rao PD. Hyma RS. Tetrahedron  1996,  52:  8001 

<A NAME="RD00508ST-1C">1c</A> Fort Y. Berthe MC. Tetrahedron  1992,  48:  6371 

<A NAME="RD00508ST-1D">1d</A> Drewes SE. Roos GHP. Tetrahedron  1988,  44:  4653 

<A NAME="RD00508ST-2A">2a</A> Ciganek E. Org. React. (N. Y.)  1997,  51:  201 

<A NAME="RD00508ST-2B">2b</A> Aggarwal VK. Dean DK. Mereu A. Williams R. J. Org. Chem.  2002,  67:  510 

<A NAME="RD00508ST-3">3</A> Gaied MM. Rezgui F. Tetrahedron Lett.  1998,  39:  5965 

<A NAME="RD00508ST-4A">4a</A> Cheng J.-P. Luo S. Zhang B. Janczuk A. He J. Wang PG. Tetrahedron Lett.  2002,  43:  7369 

<A NAME="RD00508ST-4B">4b</A> Cheng J.-P. Luo S. Wang PG. J. Org. Chem.  2004,  69:  555 

<A NAME="RD00508ST-5">5</A> Kobayashi S. Kawamura M. Tetrahedron Lett.  1999,  40:  1539 

<A NAME="RD00508ST-6A">6a</A> Kataoka T. Iwama T. Tsujiyama S. Chem. Commun.  1998,  197 

<A NAME="RD00508ST-6B">6b</A> Kataoka T. Iwama T. Tsujiyama S. Iwamura T. Watanabe S. Tetrahedron  1998,  54:  11813 

<A NAME="RD00508ST-7">7</A> Ikegami S. Yamada Y. Tetrahedron Lett.  2000,  41:  2165 

<A NAME="RD00508ST-8">8</A> Jaunch J. J. Org. Chem.  2001,  66:  609 

<A NAME="RD00508ST-9">9</A> Black GP. Dinon F. Fratucello S. Murphy PJ. Nielsen M. Williams HL. Tetrahedron Lett.  1997,  38:  8561 

<A NAME="RD00508ST-10">10</A> Barret GM. Cook AS. Kamimura A. Chem. Commun.  1998,  2533 

<A NAME="RD00508ST-11">11</A> Aggarwal VK. Mereu A. Chem. Commun.  1999,  2311 

<A NAME="RD00508ST-12">12</A> Li G. Wei H. Gao JJ. Caputo TD. Tetrahedron Lett.  2000,  41:  1 

<A NAME="RD00508ST-13">13</A> Shi M. Xu Y.-M. Zhao G.-L. Wu X.-F. Eur. J. Org. Chem.  2002,  3666 

<A NAME="RD00508ST-14">14</A> Narender P. Gangadasu B. Ravinder M. Srinivas U. Swamy GYSK. Ravikumar K. Jayathirtha Rao V. Tetrahedron  2006,  62:  954 

<A NAME="RD00508ST-15A">15a</A> Choudary BM. Kantam ML. Ranganath KVS. Sreedhar B. J. Am. Chem. Soc.  2004,  126:  3396 

<A NAME="RD00508ST-15B">15b</A> Choudary BM. Ranganath KVS. Pal U. Sreedhar B. J. Am. Chem. Soc.  2005,  127:  13167 

<A NAME="RD00508ST-15C">15c</A> Choudary BM. Chakrapani L. Ramani T. Vijay Kumar K. Kantam ML. Tetrahedron  2006,  62:  9571 

<A NAME="RD00508ST-15D">15d</A> Choudary BM. Ranganath KVS. Yadav J. Kantam ML. Tetrahedron Lett.  2005,  46:  1369 

<A NAME="RD00508ST-15E">15e</A> Kantam ML. Chakrapani L. Ramani T. Tetrahedron Lett.  2007,  48:  6121 

<A NAME="RD00508ST-16A">16a</A> Klabunde KJ. Stark J. Koper O. Mohs C. Park DG. Decker S. Jiang Y. Lagadic I. Zhang D. J. Phys. Chem.  1996,  100:  12142 

<A NAME="RD00508ST-16B">16b</A> Jeevanandam P. Klabunde KJ. Langmuir  2002,  18:  5309 

<A NAME="RD00508ST-17">17</A>

General Procedure for the Baylis-Hillman Reaction of Cyclic Enones using NAP-MgO: To a dried 25-mL round-bottomed flask charged with NAP-MgO (25 mg) were added MeOH (3 mL), followed by aldehyde (0.5 mmol) and cyclic enone (1 mmol) at r.t. The reaction was monitored by TLC. After completion of the reaction, the catalyst was separated by centrifuging the reaction mixture, and the supernatant liquid was concentrated to afford the crude product. Column chromatography of the crude (silica gel, 60-120 mesh, EtOAc-hexane, varying proportions) gave the corresponding Baylis-Hillman adduct. All the products are known compounds, which were identified by IR, ^¹H NMR spectroscopy, and mass spectrometry.