Synlett 2002(1): 0137-0139
DOI: 10.1055/s-2002-19320
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Facile and Selective Cleavage of Prenyl Esters Catalyzed by CeCl 3 ·7 H2O-NaI

J. S. Yadav*, B. V. Subba Reddy, C. Venkateshwara Rao, P. K. Chand, A. R. Prasad
Organic Chemistry Division-I, Indian Institute of Chemical Technology, Hyderabad-500 007, India
e-Mail: Yadav@iict.ap.nic.in;
Further Information

Publication History

Received 31 October 2001
Publication Date:
01 February 2007 (online)

Abstract

A highly selective cleavage of prenyl esters has been achieved in high yields using CeCl3·7 H2O-NaI in refluxing acetonitrile under neutral conditions. This method is mild and compatible with a wide variety of functional groups such as BOC, Cbz, acetate, allyl, benzyl, tetrahydropyranyl, PMB ethers, allyl, methyl, and benzyl esters present in the molecule.

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Experimental Procedure: A mixture of 3-methylbut-2-enoate (5 mmol) CeCl3·7 H2O (5 mmol) and NaI (5 mmol) in acetonitrile (15 mL) was stirred at reflux temperature for a specified time as required to complete the reaction (Table). After complete conversion, as indicated by TLC, the reaction mixture was diluted with water (15 mL) and extracted with ethyl acetate (2 × 20 mL). The combined organic layers were dried over anhyd Na2SO4, concentrated in vacuo and purified by column chromatography on silica gel (Merck, 100-200 mesh, EtOAc-hexane, 2:8) to afford pure acid. Spectral data for the compounds 1e: Liquid, 1H NMR (CDCl3): δ = 0.87 (d, 3 H, J = 6.8 Hz), 0.98 (d, 3 H, J = 6.8 Hz), 1.73 (s, 3 H), 1.78 (s, 3 H), 2.10-2.21 (m, 1 H), 4.28 (dd, 1 H, J = 5.5, 10.3 Hz), 4.60 (d, 2 H, J = 7.0 Hz), 5.10 (s, 2 H), 5.20 (brs, NH), 5.35 (m, 1 H), 7.28-7.40 (m, 5 H). MS (EI): m/z = 319 [M+]. IR (KBr): ν 3347, 2965, 1723, 1511, 1220, 988, 722 cm-1. 2e: Solid, [α]D 20 +6.3 (c 4, CHCl3), Aldrich: [α]D 20 (c 4, CHCl3). 1H NMR (CDCl3): δ = 0.85 (d, 3 H, J = 7.0 Hz), 0.99 (d, 3 H, J = 7.0 Hz), 2.10-2.23 (m, 1 H), 4.20 (m, 1 H), 5.08 (s, 2 H), 5.80 (brs, NH), 7.25-7.40 (m, 5 H). MS (EI): m/z = 251 [M+]. IR (KBr): ν 3339, 3037, 1695, 1531, 1229, 978, 729 cm-1. 1f: Liquid, 1H NMR (CDCl3): δ = 1.40 (d, 3 H, J = 6.8 Hz), 1.78 (s, 3 H), 1.80 (s, 3 H), 4.38 (m, 1 H), 4.60 (d, 2 H, J = 7.0 Hz), 5.10 (s, 2 H), 5.37 (m, 1 H), 5.45 (brs, NH), 7.37-7.40 (m, 5 H). MS (EI): m/z = 291 [M+]. IR (KBr): ν 3342, 3035, 2965, 1724, 1525, 1453, 1209, 1065, 917, 735 cm-1. 2f: Solid, [α]D 20 -13.9 (c 2, HOAc), Aldrich: [α]D 23 -14.2 (c 2, HOAc). 1H NMR (DMSO-d6): δ = 1.48 (d, 3 H, J = 7.0 Hz), 4.40 (m, 1 H), 5.18 (s, 2 H), 5.27 (brs, NH), 7.28-7.40 (m, 5 H), 8.15 (brs, OH). MS (EI): m/z = 223 [M+]. IR (KBr): ν 3333, 3036, 1695, 1536, 1458, 1252, 1075, 1027, 914, 739 cm-1.

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