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.
Keywords
Baylis-Hillman reaction - cyclic enones - NAP-MgO - heterogeneous - solid base
References and Notes
1a Mortia K.
Suzuki Z.
Hirose H.
Bull. Chem. Soc. Jpn.
1968,
41:
2815
1b Basavaiah D.
Rao PD.
Hyma RS.
Tetrahedron
1996,
52:
8001
1c Fort Y.
Berthe MC.
Tetrahedron
1992,
48:
6371
1d Drewes SE.
Roos GHP.
Tetrahedron
1988,
44:
4653
2a Ciganek E.
Org. React. (N. Y.)
1997,
51:
201
2b Aggarwal VK.
Dean DK.
Mereu A.
Williams R.
J. Org.
Chem.
2002,
67:
510
3 Gaied MM.
Rezgui F.
Tetrahedron Lett.
1998,
39:
5965
4a Cheng J.-P.
Luo S.
Zhang B.
Janczuk A.
He J.
Wang PG.
Tetrahedron Lett.
2002,
43:
7369
4b Cheng J.-P.
Luo S.
Wang PG.
J.
Org. Chem.
2004,
69:
555
5 Kobayashi S.
Kawamura M.
Tetrahedron Lett.
1999,
40:
1539
6a Kataoka T.
Iwama T.
Tsujiyama S.
Chem. Commun.
1998,
197
6b Kataoka T.
Iwama T.
Tsujiyama S.
Iwamura T.
Watanabe S.
Tetrahedron
1998,
54:
11813
7 Ikegami S.
Yamada Y.
Tetrahedron Lett.
2000,
41:
2165
8 Jaunch J.
J.
Org. Chem.
2001,
66:
609
9 Black GP.
Dinon F.
Fratucello S.
Murphy PJ.
Nielsen M.
Williams HL.
Tetrahedron Lett.
1997,
38:
8561
10 Barret GM.
Cook AS.
Kamimura A.
Chem.
Commun.
1998,
2533
11 Aggarwal VK.
Mereu A.
Chem. Commun.
1999,
2311
12 Li G.
Wei H.
Gao JJ.
Caputo TD.
Tetrahedron Lett.
2000,
41:
1
13 Shi M.
Xu Y.-M.
Zhao G.-L.
Wu X.-F.
Eur. J. Org. Chem.
2002,
3666
14 Narender P.
Gangadasu B.
Ravinder M.
Srinivas U.
Swamy GYSK.
Ravikumar K.
Jayathirtha Rao V.
Tetrahedron
2006,
62:
954
15a Choudary BM.
Kantam ML.
Ranganath KVS.
Sreedhar B.
J. Am. Chem. Soc.
2004,
126:
3396
15b Choudary BM.
Ranganath KVS.
Pal U.
Sreedhar B.
J.
Am. Chem. Soc.
2005,
127:
13167
15c Choudary BM.
Chakrapani L.
Ramani T.
Vijay Kumar K.
Kantam ML.
Tetrahedron
2006,
62:
9571
15d Choudary BM.
Ranganath KVS.
Yadav J.
Kantam ML.
Tetrahedron Lett.
2005,
46:
1369
15e Kantam ML.
Chakrapani L.
Ramani T.
Tetrahedron Lett.
2007,
48:
6121
16a Klabunde KJ.
Stark J.
Koper O.
Mohs C.
Park DG.
Decker S.
Jiang Y.
Lagadic I.
Zhang D.
J. Phys. Chem.
1996,
100:
12142
16b Jeevanandam P.
Klabunde KJ.
Langmuir
2002,
18:
5309
17
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, ¹ H NMR spectroscopy, and mass spectrometry.
