Abstract
Sm/TiCl4 system could well integrate the high reactivity of samarium(II) and high deoxygenation capacity of low valent titanium within one system. In this paper, the intermolecular and intramolecular reductive coupling reactions of ketones with esters mediated by metallic samarium (Sm) and a catalytic amount of titanium tetrachloride (TiCl4) were successfully developed. A series of substituted ketones and cyclic β-keto-esters were prepared in moderate to good yields under reflux and neutral conditions.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Fürstner, A., Bogdanović, B., 1996. New developments in the chemistry of low-valent titanium. Angew. Chem. Int. Ed., Engl., 35(21):2442–2469. [doi:10.1002/anie.199624421]
Girard, P., Namy, J.L., Kagan, H.B., 1980. Divalent lanthanide derivatives in organic synthesis. 1. Mild preparation of samarium iodide and ytterbium iodide and their use as reducing or coupling agents. J. Am. Chem. Soc., 102(8):2693–2698. [doi:10.1021/ja00528a029]
Henze, H.R., Leslie, W.B., 1950. Synthesis of 5-benzohydryl-5-substituted hydantoins. J. Org. Chem., 15(4):901–907. [doi:10.1021/jo01150a031]
Koelsch, C.F., 1932. Phenyl-para-tolylacetophenone. J. Am. Chem. Soc., 54(5):2049–2052. [doi:10.1021/ja01344a053]
Krief, A., Laval, A.M., 1999. Coupling of organic halides with carbonyl compounds promoted by SmI2, the Kagan reagent. Chem. Rev., 99(3):745–778. [doi:10.1021/cr980326e]
Lenoir, D., 1989. The application of low-valent titanium reagents in organic synthesis. Synthesis, (12):883–897. [doi:10.1055/s-1989-27424]
Li, Z.F., Zhang, Y.M., 2001. Samarium diiodide mediated coupling of aroyl chlorides. Chin. J. Chem., 19(6): 634–636.
Li, Z.F., Zhang, Y.M., Liu, Y.K., 2002. Sm/TiCl4 system induced reductive coupling reactions: synthesis of tetraarylfurans. J. Indian Chem. Soc., 79(2):188–189.
Liu, Y.K., Zhang, Y.M., 2001. Intermolecular and Intramolecular ketone-ester reductive coupling reactions promoted by samarium(II) iodide. Tetrahedron Lett., 42(33):5745–5748. [doi:10.1016/S0040-4039(01)01107-8]
Liu, X., Liu, Y.K., Zhang, Y.M., 2002. A novel method for the synthesis of vicinal disulfonamides promoted by metallic samarium in aqueous media. Tetrahedron Lett., 43(38):6787–6789. [doi:10.1016/S0040-4039(02)01509-5]
Liu, Y.K., Zheng, H., Xu, D.Q., Xu, Z.Y., Zhang, Y.M., 2006. Sm/I2 (trace) system-mediated selective cleavage of the S-S or C-S bonds in sodium (Z)-allyl thiosulfates under aqueous media: selective formation of Di(Z-allyl) disulfides or (2E)-methyl cinnamic esters. Synlett., (15):2492–2494.
Ma, Y.M., Zhang, Y.M., 2000. Reductive coupling of ketones with imines promoted by titanium-tetrachloride/samarium system. Org. Prep. Precd. Int., 32(6):567–570.
Ma, Y.M., Zhang, Y.M., Zhou, L.H., 2000. Samarium(II) iodide promoted reductive coupling of ketones and imines. J. Chem. Res.(S), (5):250–251.
McMurry, J.E., 1974. Organic chemistry of low-valent titanium. Acc. Chem. Res., 7(9):281–286. [doi:10.1021/ar50081a001]
McMurry, J.E., 1983. Titanium-induced dicarbonyl-coupling reactions. Acc. Chem. Res., 16(11):405–411. [doi:10. 1021/ar00095a003]
McMurry, J.E., 1989. Carbonyl-coupling reactions using low-valent titanium. Chem. Rev., 89(7):1513–1524. [doi:10.1021/cr00097a007]
Molander, G.A., 1992. Application of lanthanide reagents in organic synthesis. Chem. Rev., 92(1):29–68. [doi:10.1021/ cr00009a002]
Molander, G.A., Harris, C.R., 1996. Sequencing reactions with samarium(II) iodide. Chem. Rev., 96(1):307–338. [doi:10.1021/cr950019y]
Nagano, J., 1955. Triphenylethylene derivatives. I. J. Am. Chem. Soc., 77(6):1691–1692. [doi:10.1021/ja01611a093]
Shi, D.Q., Chen, J.X., Chai, W.Y., Chen, W.X., Kao, T.Y., 1993. Low-valent titanium induced reductive coupling reaction of carboxylic derivatives with aromatic ketones. Tetrahedron Lett., 34(18):2963–2964. [doi:10.1016/S0040-4039(00)60493-8]
Zhang, Y.M., Liu, Y.K., 2001. Application of Sm0/auxiliary and Sm0/MCln system in organic synthesis. Chin. J. Chem., 19(2):123–130.
Zhou, L.H., Zhang, Y.M., 1998a. Low-valent titanium induced reductive coupling of nitriles with nitro compounds. Synth. Commun., 28(17):3249–3262.
Zhou, L.H., Zhang, Y.M., 1998b. Samarium(II) iodide induced reductive coupling of nitriles with nitro compounds. J. Chem. Soc., Perkin Trans. 1, (17):2899–2902. [doi:10.1039/a803077d]
Zhou, L.H., Zhang, Y.M., 1998c. Samarium(II) iodide promoted novel reductive coupling of ketones and nitriles. Tetrahedron Lett., 39(46):8491–8494. [doi:10.1016/S0040-4039(98)01984-4]
Zhou, L.H., Zhang, Y.M., 2000. Intermolecular and intramolecular ketone-nitrile reductive coupling reactions promoted by TiCl4-Sm system. Tetrahedron, 56(19):2953–2960. [doi:10.1016/S0040-4020(00)00077-6]
Author information
Authors and Affiliations
Corresponding author
Additional information
Project (No. 2004C21032) supported by the Key Technologies R & D Program of Zhejiang Province, China
Rights and permissions
About this article
Cite this article
Liu, Yk., Xu, Dq., Xu, Zy. et al. Sm/TiCl4 (cat.) system-mediated intermolecular and intramolecular reductive coupling reactions of ketones with esters. J. Zhejiang Univ. - Sci. A 8, 999–1003 (2007). https://doi.org/10.1631/jzus.2007.A0999
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1631/jzus.2007.A0999