CLC number: O641.6
On-line Access:
Received: 2005-11-21
Revision Accepted: 2005-12-21
Crosschecked: 0000-00-00
Cited: 1
Clicked: 5767
Liu Yun-Kui, Zheng Hui, Xu Dan-Qian, Xu Zhen-Yuan, Zhang Yong-Min. Remarkable rate acceleration of SmI3-mediated iodination of acetates of Baylis-Hillman adducts in ionic liquid: facile synthesis of (Z)-allyl iodides[J]. Journal of Zhejiang University Science B, 2006, 7(3): 193-197.
@article{title="Remarkable rate acceleration of SmI3-mediated iodination of acetates of Baylis-Hillman adducts in ionic liquid: facile synthesis of (Z)-allyl iodides",
author="Liu Yun-Kui, Zheng Hui, Xu Dan-Qian, Xu Zhen-Yuan, Zhang Yong-Min",
journal="Journal of Zhejiang University Science B",
volume="7",
number="3",
pages="193-197",
year="2006",
publisher="Zhejiang University Press & Springer",
doi="10.1631/jzus.2006.B0193"
}
%0 Journal Article
%T Remarkable rate acceleration of SmI3-mediated iodination of acetates of Baylis-Hillman adducts in ionic liquid: facile synthesis of (Z)-allyl iodides
%A Liu Yun-Kui
%A Zheng Hui
%A Xu Dan-Qian
%A Xu Zhen-Yuan
%A Zhang Yong-Min
%J Journal of Zhejiang University SCIENCE B
%V 7
%N 3
%P 193-197
%@ 1673-1581
%D 2006
%I Zhejiang University Press & Springer
%DOI 10.1631/jzus.2006.B0193
TY - JOUR
T1 - Remarkable rate acceleration of SmI3-mediated iodination of acetates of Baylis-Hillman adducts in ionic liquid: facile synthesis of (Z)-allyl iodides
A1 - Liu Yun-Kui
A1 - Zheng Hui
A1 - Xu Dan-Qian
A1 - Xu Zhen-Yuan
A1 - Zhang Yong-Min
J0 - Journal of Zhejiang University Science B
VL - 7
IS - 3
SP - 193
EP - 197
%@ 1673-1581
Y1 - 2006
PB - Zhejiang University Press & Springer
ER -
DOI - 10.1631/jzus.2006.B0193
Abstract: Stereoselective transformation of Baylis-Hillman acetates 1 into corresponding (Z)-allyl iodides 2 has been achieved by treatment of 1 with samarium triiodide in THF. Remarkable rate acceleration of samarium triiodide-mediated iodination of 1 was found when ionic liquid 1-n-butyl-3-methyl-imidazolium tetrafluroborate ([bmim]BF4) was used as reaction media in stead of THF. This novel approach proceeds readily at 50 °C within a few minutes to afford (Z)-allyl iodides 2 in excellent yields. A mechanism involving stereoselective iodination of the acetates of baylis-Hillman adducts by samarium triiodide is described, in which a six-membered ring transition state played a key role in the stereoselective formation of 2.
[1] Ameer, F., Drewes, S.E., Houston-McMillan, M.S., Kaye, P.T., 1985. Necic acid synthons. Part. 4. Regeoselectivity in the reactions of chloro and iodo derivatives of selected 3-hydroxy-2-methylenealkanoate esters with ethyl 2-methyl-3-oxobutanoate. J. Chem. Soc., Perkin Trans. 1, (6):1143-1146.
[2] Basavaiah, D., Bhavani, A.K.D., Pandiaraju, S., Sarma, P.K.S., 1995. Baylis-Hillman reaction: magnesium bromide as a stereoselective reagent for the synthesis of [E]- and [Z]-allyl bromides. Synlett., (3):243-244.
[3] Basavaiah, D., Rao, P.D., Hyma, R.S., 1996a. The Baylis-Hillman reaction: a novel carbon-carbon bond forming reaction. Tetrahedron, 52(24):8001-8062.
[4] Basavaiah, D., Pandiaraju, S., Padmaja, K., 1996b. The Friedel-Crafts chemistry: acetates of the Baylis-Hillman adducts as novel stereodefined β-electrophiles. Synlett., (4):393-395.
[5] Basavaiah, D., Bakthadoss, M., Pandiaraju, S., 1998. A new protocol for the syntheses of (E)-3-benzylidenechroman-4-ones: a simple synthesis of the methyl ether of bonducellin. J. Chem. Soc., Chem. Commun., (16):1639-1640.
[6] Basavaiah, D., Rao, A.J., Satyanarayana, T., 2003. Recent advances in the Baylis-Hillman reaction and applications. Chem. Rev., 103(3):811-891.
[7] Buchholz, R., Hoffmann, H.M.R., 1991. α-methylidene- and α-alkylidene-β-lactams from nonproteinogenic amino acids. Helv. Chim. Acta, 74(6):1213-1220.
[8] Chavan, S.P., Ethiraj, K.S., Kamat, S.K., 1997. Facile synthesis of 2E-2-chloromethyl aryl-2-enoates. Tetrahedron Lett., 38(42):7415-7416.
[9] Chen, J., Zhang, Y.M., 2004. Reductive cyclodimerization of arylmethylidenemalononitriles promoted by samarium and catalytic amount of iodine: facile synthesis of cyclopentene derivatives. Zhejiang Univ. SCI, 5(2):218-221.
[10] Cho, C.W., Krische, M.J., 2004. Regio- and stereoselective construction of γ-butenolides through phosphine-catalyzed substitution of Morita-Baylis-Hillman acetates: an organocatalytic allylic alkylation. Angew. Chem., Int. Ed., 43(48):6689-6691.
[11] Chung, Y.M., Gong, J.H., Kim, T.H., Kim, J.N., 2001. Synthesis of ethyl 3-cyano-2-methylcinnamates and 3-cyano-2-methylcinnamonitriles from the Baylis-Hillman acetates. Tetrahedron Lett., 42(51):9023-9026.
[12] Concellón, J.M., Bernad, P.J., Pére-Andrés, J.A., 1999. Samarium mediated β-elimination in dihalo alcohols: diastereoselective synthesis of (Z)-vinyl halides. Angew. Chem., Int. Ed., 38(16):2384-2386.
[13] Fan, X.S., Zhang, Y.M., 2002. Samarium triiodide mediated dethiocyanation of phenacyl thiocyanates and its application in carbon-carbon bond formation reactions. J. Chem. Res. (S), 9:439-441.
[14] Hoffmann, H.M.R., Rabe, J., 1985. Synthesis and biological activity of α-methylene-γ-butyrolactones. Angew. Chem. Int. Ed., 24(2):94-110.
[15] Kabalka, G.W., Venkataiah, B., Dong, G., 2003. Preparation of substituted allyl acetates and sulfones from Baylis-Hillman adducts in ionic liquid media. Tetrahedron Lett., 44(25):4673-4675.
[16] Kabalka, G.W., Venkataiah, B., Dong, G., 2004. Pd-catalyzed cross-coupling of Baylis-Hillman acetate adducts with bis(pinacolato)diboron: an efficient route to functionalized allyl borates. J. Org. Chem., 69(17):5807-5809.
[17] Li, J., Qian, W.X., Zhang, Y.M., 2004. SmI2-mediated elimination reaction of Baylis-Hillman adducts controlled by temperature: a facile synthesis of trisubstituted alkenes and 1,5-hexadiene derivatives with E-selectivity. Tetrahedron, 60(27):5793-5798.
[18] Li, J., Wang, X.X., Zhang, Y.M., 2005a. Direct and highly efficient synthesis of (Z)-allyl iodides from Baylis-Hillman adducts promoted by TMSCl/NaI system. Synlett., (6):1039-1040.
[19] Li, J., Wang, X.X., Zhang, Y.M., 2005b. Remarkable rate acceleration of water-promoted nucleophilic substitution of Baylis-Hillman acetates: a facile and highly efficient synthesis of N-substituted imidazole. Tetrahedron Lett., 46(31):5233-5237.
[20] Li, J., Xu, H., Zhang, Y.M., 2005c. Metallic samarium and iodine promoted facile and efficient syntheses of trisubstituted alkenes from the acetates of Baylis-Hillman adducts. Tetrahedron Lett., 46(11):1931-1934.
[21] Lu, G.L., Zhang, Y.M., 1999. Facile formation of samarium(III) selenolates from potassium iodide catalyzed reaction of samarium metal and diselenides, and their application in synthesis of selenoesters. Synth. Commun., 29(2):219-225.
[22] Ma, Y.M., Zhang, Y.M., 2003. Samarium(III) iodide promoted three component coupling reactions of aldehydes, α-haloketones, and active methylene or methyl compounds. Synth. Commun., 33(5):711-715.
[23] Sheldon, R., 2001. Catalytic reactions in ionic liquids. Chem. Commun., 23:2399-2407.
[24] Wasserscheid, P., Keim, W., 2000. Ionic liquids-new “solution” for transition metal catalysis. Angewandte Chemie, 39(21):3772-3789.
[25] Welton, T., 1999. Room-temperature ionic liquids. Solvents for synthesis and catalysis. Chem. Rev., 99(8):2071-2083.
[26] Yadav, J.S., Reddy, B.V.S., Madan, C., 2001. Montmorillonite clay-catalyzed stereoselective syntheses of aryl-substituted (E)-and (Z)-allyl iodides and bromides. New J. Chem., 25(9):1114-1117.
[27] Zhang, Y.M., Liu, Y.K., 2001. Application of samarium reagents in organic synthesis. You Ji Hua Xue, 21(11):962-973 (in Chinese).
[28] Zhou, L.H., Zhang, Y.M., 1997. A novel cyclodimerization of arylidenecyanoacetate promoted by samarium diiodide. Tetrahedron Lett., 38(46):8063-8066.
Open peer comments: Debate/Discuss/Question/Opinion
<1>