Oxidative [3+2] Cycloaddition Reactions of 1,3-Dicarbonyl Compounds to Exocyclic Alkenes: The Regiospecific Synthesis of Spirodihydrofurans

Sengodagounder Muthusamy; Chidambaram Gunanathan; Srinivasarao Arulananda Babu

doi:10.1055/s-2002-25334

LETTER

Oxidative [3+2] Cycloaddition Reactions of 1,3-Dicarbonyl Compounds to Exocyclic Alkenes: The Regiospecific Synthesis of Spirodihydrofurans

Sengodagounder Muthusamy*, Chidambaram Gunanathan, Srinivasarao Arulananda Babu
Silicates and Catalysis Discipline, Central Salt and Marine Chemicals Research Institute, Bhavnagar 364 002, India
Fax: +91(278)567562, +91(278)566970; e-Mail: salt@csir.res.in;

Abstract

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Abstract

Regiospecific synthesis of a variety of spirodihydrofurans was achieved using cerium(IV) ammonium nitrate mediated oxidative [3+2] cycloaddition of 1,3-dicarbonyl compounds to exocyclic olefins.

Key words

alkenes - cerium(IV) ammonium nitrate - 1,3-dicarbonyl compounds - oxidative cycloaddition - spirodihydrofuran

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References

<A NAME="RD02302ST-1A">1a</A> Surzur J.-M. In Reactive Intermediates Vol. 2: Abramovitch RA. Plenum; New York: 1982. p.121-295

<A NAME="RD02302ST-1B">1b</A> Giese B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds Pergamon; Oxford: 1986.

<A NAME="RD02302ST-2A">2a</A> Snider BB. Chem. Rev. 1996, 96: 339

<A NAME="RD02302ST-2B">2b</A> Iqbal J. Bhatia B. Nayyar NK. Chem. Rev. 1994, 94: 519

<A NAME="RD02302ST-2C">2c</A> Klein WJ. In Organic Synthesis by Oxidation with Metal Compounds Mijs WJ. de Jonge CRH. Plenum; New York: 1986.

<A NAME="RD02302ST-3">3</A> Heiba EI. Dessau RM. J. Am. Chem. Soc. 1972, 94: 2888

<A NAME="RD02302ST-4">4</A> Nair V. Mathew J. Prabhkaran J. Chem. Soc. Rev. 1997, 127

<A NAME="RD02302ST-5A">5a</A> Linker T. Sommermann T. Kahlenberg F. J. Am. Chem. Soc. 1997, 119: 9377

<A NAME="RD02302ST-5B">5b</A> Linker T. Hartmann K. Sommermann T. Scheutzow D. Ruckdeschel E. Angew. Chem., Int. Ed. Engl. 1996, 35: 1730

<A NAME="RD02302ST-6A">6a</A> Nair V. Mathew J. J. Chem. Soc., Perkin Trans. 1 1995, 187

<A NAME="RD02302ST-6B">6b</A> Nair V. Mathew J. Radhakrishnan KV. J. Chem. Soc., Perkin Trans. 1 1996, 1487

<A NAME="RD02302ST-7">7</A> Lee YR. Kim BS. Kim DH. Tetrahedron 2000, 56: 8845

<A NAME="RD02302ST-8">8</A> Roy SC. Mandal PK. Tetrahedron 1996, 52: 2193

<A NAME="RD02302ST-9">9</A> Roy SC. Mandal PK. Tetrahedron 1996, 52: 12495

<A NAME="RD02302ST-10">10</A> Hong B.-C. Sun H.-I. Shr Y.-J. Lin K.-J. J. Chem. Soc., Perkin Trans. 1 2000, 2939

<A NAME="RD02302ST-11">11</A> Lee YR. Kim BS. Tetrahedron Lett. 1997, 38: 2095

<A NAME="RD02302ST-12A">12a</A> Gerwick WH. Fenical W. J. Org. Chem. 1981, 46: 22

<A NAME="RD02302ST-12B">12b</A> Sakai K. Watanabe K. Masuda K. Tsuji M. Hasumi K. Endo A. J. Antibiot. 1995, 48: 447

<A NAME="RD02302ST-13A">13a</A> Muthusamy S. Gunanathan C. Babu SA. Tetrahedron Lett. 2001, 42: 523

<A NAME="RD02302ST-13B">13b</A> Muthusamy S. Babu SA. Gunanathan C. Suresh E. Dastidar P. Jasra RV. Tetrahedron 2001, 57: 7009

<A NAME="RD02302ST-13C">13c</A> Muthusamy S. Babu SA. Gunanathan C. Suresh E. Dastidar P. Synlett 2001, 1407

<A NAME="RD02302ST-13D">13d</A> Muthusamy S. Babu SA. Gunanathan C. Tetrahedron Lett. 2000, 41: 8839

<A NAME="RD02302ST-13E">13e</A> Muthusamy S. Babu SA. Gunanathan C. Suresh E. Dastidar P. Jasra RV. Tetrahedron 2000, 56: 6307

<A NAME="RD02302ST-14">14</A> Greenwald R. Chaykovsky M. Corey EJ. J. Org. Chem. 1963, 28: 1128

General procedure for the synthesis of spirodihydrofurans: A solution of CAN (2.2 mmol) in methanol (10 mL) was added to a methanolic solution (10 mL) containing exocyclic olefin (1 mmol) and 1,3-dicarbon-yl compound (1.2 mmol) at 0 °C with stirring under an argon atmosphere. The reaction proceeds rapidly and the reddish brown color of CAN disappears by the time the addition was over. After decolorization, the reaction mixture was diluted with water (50 mL) and extracted using dichloromethane
(3 × 30 mL). The combined organic extracts were washed with water and brine, dried over anhydrous magnesium sulfate and concentrated. The residue was purified through silica gel column chromatography (10% ethyl acetate-hexane) to furnish spirodihydrofurans (8a-p).

All new compounds gave satisfactory spectroscopic data consistent with their structures. Selected spectral data, 8a: Yellow solid, mp 69-70 °C; IR (CHCl₃): = 2909, 1667, 1598, 1452, 1390, 1245, 1154, 1102, 1064, 983, 937, 918, 733 cm^-1; ¹H NMR (200 MHz, CDCl₃): δ = 1.57-1.62 (m, 2 H), 1.74-1.83 (m, 10 H), 2.15-2.23 (m, 8 H), 2.78 (s, 2 H); ¹³C NMR (50.3 MHz, CDCl₃): δ = 16.1 (CH₃), 26.1 (CH), 29.8 (CH₃), 33.6 (CH₂), 35.1 (CH₂), 37.7 (CH), 38.0 (CH₂), 41.0 (CH₂), 92.9 (quat-C, C-5), 112.5 (quat-C, C-3), 169.2 (quat-C, C-2), 195.1 (quat-C, C=O); MS: m/z = 246 (M⁺); Anal. Calcd for C₁₆H₂₂O₂: C, 78.01; H, 9.00. Found: C, 78.05; H, 8.98. 8m: Yellow solid; mp 83-84 °C; IR (CHCl₃): = 2928, 1679, 1603, 1467, 1378, 1258, 1144, 1073, 937, 631 cm^-1; ¹H NMR (200 MHz, CDCl₃): δ = 0.89 (s, 3 H, CH₃), 0.97 (s, 3 H, CH₃), 1.01 (s, 3 H, CH₃), 1.09-1.63 (m, 9 H), 1.65-1.80 (m, 3 H), 2.18-2.23 (m, 8 H), 2.88 (d, 1 H, J = 6.0 Hz); ¹³C NMR (50.3 MHz, CDCl₃, mixture of diastereomer, * denotes minor isomer): δ = 15.4* (CH₃), 15.6 (CH₃), 21.3* (CH₂), 22.1 (CH₂), 24.0* (CH₂), 24.6 (CH₂), 24.8 (CH₂), 24.9* (CH₂), 25.5 (CH₃), 28.5* (CH₂), 29.6 (CH₃), 29.7 (CH₃), 30.8* (CH₃), 31.4* (CH₃), 32.9* (CH₂), 33.4 (quat-C), 33.5 (quat-C), 34.1 (CH₃), 35.5* (CH₂), 37.6* (CH₂), 38.5 (CH₂), 38.8 (CH₂), 39.3* (CH₂), 41.0* (CH₂), 45.7 (CH), 48.0 (quat-C), 49.5 (CH), 51.4* (CH), 63.5 (CH), 113.1 (quat-C), 166.5 (quat-C), 194.7 (quat-C, C=O). MS: m/z = 303 (M + 1, 43.5), 302 (M⁺, 76.5), 287 (22.6), 260(100), 241 (35.7), 217 (28.7), 190 (40.9), 189(72), 164(44), 150 (61.7), 119 (69.6), 105(79), 91 (74.8), 67 (74.8); Anal. Calcd for C₂₀H₃₀O₂: C, 79.42; H, 10.00. Found: C, 79.48; H, 9.97.