Abstract
γ-Hydroxy-α,β-unsaturated nitrile was obtained by the reaction of α-arylsulfinylacetonitrile with aldehyde in water, which was catalyzed by N ,N -diethylaminopropylated silica gel. The overall transformation proceeded via five sequential reactions, 1,2-addition of acetonitrile, dehydration (Knoevenagel condensation), isomerization of the double bond, rearrangement of sulfinyl group (Mislow-Evans rearrangement) and hydrolysis of sulfinyl ester. The reaction condition was mild such that the AcO, TBMDSO or OTHP group remained intact in the products.
Key words
green chemistry - aqueous reaction - condensation - rearrangement - supported catalysis - sulfoxides
References and Notes
1 Anastas PT.
Warner JC.
Green Chemistry: Theory and Practice
Oxford University Press;
Oxford:
1998.
2 Dalko PI.
Moisan L.
Angew. Chem. Int. Ed.
2004,
43:
5138
3a Isobe K.
Hoshi T.
Suzuki T.
Hagiwara H.
Mol. Diversity
2005,
9:
317
3b Hagiwara H.
Hamaya J.
Hoshi T.
Yokoyama C.
Tetrahedron Lett.
2005,
46:
393
3c Fukushima M.
Endou S.
Hoshi T.
Suzuki T.
Hagiwara H.
Tetrahedron Lett.
2005,
46:
3287
3d Hagiwara H.
Koseki A.
Isobe K.
Shimizu K.
Hoshi T.
Suzuki T.
Synlett
2004,
2188
3e Shimizu K.
Suzuki H.
Kodama T.
Hagiwara H.
Kitayama Y.
Stud. Surf. Sci. Catal.
2003,
145:
145
3f Hamaya J.
Suzuki T.
Hoshi T.
Shimizu K.
Kitayama Y.
Hagiwara H.
Synlett
2003,
873
3g Shimizu K.
Hayashi E.
Inokuchi T.
Kodama T.
Hagiwara H.
Kitayama Y.
Tetrahedron Lett.
2002,
43:
9073
3h Hagiwara H.
Tsuji S.
Okabe T.
Hoshi T.
Suzuki T.
Suzuki H.
Shimizu K.
Kitayama Y.
Green Chem.
2002,
4:
461
3i Shimizu K.
Suzuki H.
Hayashi E.
Kodama T.
Tsuchiya Y.
Hagiwara H.
Kitayama Y.
Chem. Commun.
2002,
1068
4 Nokami J.
Mandai T.
Imakura Y.
Nishiuchi K.
Kawada M.
Wakabayashi S.
Tetrahedron Lett.
1981,
22:
4489
5a Evans DA.
Andrews GC.
Acc. Chem. Res.
1974,
7:
147
5b Evans DA.
Andrews GC.
J. Am. Chem. Soc.
1972,
94:
3672
5c Tang R.
Mislow K.
J. Am. Chem. Soc.
1970,
92:
2100
5d Bickart P.
Carson FW.
Jacobus J.
Miller EG.
Mislow K.
J. Am. Chem. Soc.
1968,
90:
4869
6a Nokami J.
Kataoka K.
Shiraishi K.
Osafune M.
Hussain I.
Sumida S.-I.
J. Org. Chem.
2001,
66:
1228
6b Bonini BF.
Franchini MC.
Mazzanti G.
Slief
J.-W.
Wegman MA.
Zwanenburg B.
Chem. Commun.
1997,
1011
6c Nokami J.
Taniguchi A.
Honda M.
Fukutake S.
Chem. Lett.
1995,
1025 ; and earlier references cited therein
7a Trost BM.
Dong L.
Schroeder M.
J. Am. Chem. Soc.
2005,
127:
2844
7b Charest MG.
Lerner CD.
Brubaker JD.
Siegel DR.
Myers AG.
Science
2005,
308:
395
7c Mapp AK.
Heathcock CH.
J. Org. Chem.
1999,
64:
23
7d Nokami J.
Osafune M.
Shiraishi K.
Sumida S.
Imai N.
J. Chem. Soc., Perkin Trans. 1
1997,
2947
7e Nokami J.
Taniguchi T.
Ogawa Y.
Chem. Lett.
1995,
43
7f Jones-Hertzog DK.
Jorgensen WL.
J. Org. Chem.
1995,
60:
6682
7g Posner GH.
Haces A.
Harrison W.
Kinter CM.
J. Org. Chem.
1987,
52:
4836
7h Ono T.
Tamaoka T.
Yuasa Y.
Matsuda T.
Nokami J.
Wakabayashi S.
J. Am. Chem. Soc.
1984,
106:
7890
7i Mandai T.
Osaka K.
Kawaguchi M.
Kawada M.
Otera J.
J. Org. Chem.
1984,
49:
3595
7j Reich HJ.
Wollowitz S.
J. Am. Chem. Soc.
1982,
104:
7051
8 Nokami J.
Mandai T.
Nishimura A.
Takeda T.
Wakabayashi S.
Kunieda N.
Tetrahedron Lett.
1986,
27:
5109
9a Li C.-J.
Chem. Rev.
2005,
105:
3095
9b Wilson EK.
Chem. Eng. News
2005,
49
9c Lindstrom UM.
Chem. Rev.
2002,
102:
275
9d Ribe S.
Wipf P.
Chem. Commun.
2001,
299 ; and earlier references cited in these references
10
Typical Experimental Procedure.
2 O (1 mL) was added m -chloro-phenylacetonitrile (102 mg, 0.52 mmol) under nitrogen atmosphere. After being stirred for 10 min, (+)-citronellal (63 µL, 0.35 mmol) was added and stirring was continued for 6 h at r.t. After addition of 10% aq Et2 NH (30 µL, 0.029 mmol), the mixture was stirred for 10 min. Product was triturated with EtOAc four times under vigorous stirring. The combined organic layer was evaporated to dryness and the residue was purified by medium pressure LC (eluent: EtOAc-n -hexane = 1:2) to give a diastereomeric mixture of (2E )-4-hydroxy-5,9-dimethyldeca-2,8-dienenitrile (54 mg, 80%).
