Cerium(IV) Ammonium Nitrate (CAN): A Very Efficient Reagent for the Synthesis of Tertiary Ethers

Abstract

Treatment of tertiary 1,4- and 1,5-diols with cerium ammonium nitrate at room temperature led to the corresponding tetrahydrofuran and tetrahydropyran derivatives in high yield and stereoselectivity. Utilizing this methodology, manoyl oxide (25a) and a variety of fragrant compounds, such as linalool oxide (8), caparrapi oxide (12), ambrox (14) and other related amber-gris-type odorants have been synthesized; 16 examples are described.

Key words

cyclizations - diols - ethers - natural products - stereo­selectivity

References and Notes

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35

Typical Experimental Procedure. To a deoxygenated solution of compound (1 mmol) in MeCN (10 mL) was added solid CAN (1.2 mmol) and the mixture was stirred under an argon atmosphere at r.t. for the specified time (Table [1] ). The progress of the reaction was monitored by TLC. After completion of the reaction, the solvent was removed and the residue was diluted with Et₂O (20 mL), washed with H₂O, brine and dried over anhyd Na₂SO₄. After removal of the solvent the residue was subjected to column chromatography on silica gel. Elution with 5% Et₂O-hexane afforded the pure product.

36

All new compounds were fully characterized spectroscopically and had satisfactory HRMS data.
Selected data:
Compound 23: ¹H NMR (400 MHz, CDCl₃): δ = 1.28 (s, 3 H), 1.19 (s, 3 H), 0.85 (t, J = 3.8 Hz, 3 H), 0.85 (s, 3 H), 0.79 (s, 3 H), 0.76 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 74.6 (C), 72.9 (C), 58.3 (CH), 56.5 (CH), 43.1 (CH₂), 42.2 (CH₂), 39.2 (CH₂), 37.9 (CH₂), 36.9 (C), 35.7 (CH₂), 33.4 (CH₃), 33.3 (C), 27.3 (CH₃), 24.9 (CH₃), 21.3 (CH₃), 19.9 (CH₂), 18.7 (CH₂), 15.8 (CH₃), 15.4 (CH₂), 8.1 (CH₃). IR (film): 1638, 1463, 1374, 1278, 1119, 1006, 959, 845 cm^-1. MS (EI) m/z (relative intensity) = 292 (3), 263 (22), 245 (100), 223 (5), 177 (18), 137 (34), 123 (23). HRMS (FAB): m/z calcd for C₂₀H₃₆ONa: 315.2664; found: 315.2650.
Compound 29: ¹H NMR (400 MHz, CDCl₃): δ = 3.90 (d, J = 10.8 Hz, 1 H), 3.72 (d, J = 10.8 Hz, 1 H), 2.06 (s, 3 H), 1.26 (s, 3 H), 1.21 (s, 3 H), 0.84 (s, 3 H), 0.77 (s, 3 H), 0.75 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 171.2 (C), 75.2 (C), 72.9 (CH₂), 71.8 (C), 57.5 (CH), 56.5 (CH), 43.0 (CH₂), 42.2 (CH₂), 39.1 (CH₂), 36.9 (C), 33.7 (CH₂), 33.4 (CH₃), 33.3 (C), 25.0 (CH₃), 24.8 (CH₃), 21.4 (CH₃), 21.2 (CH₃), 19.9 (CH₂), 18.6 (CH₂), 15.7 (CH₃), 14.9 (CH₃). IR (film): 1744, 1464, 1377, 1241, 1122, 1044, 994, 757 cm^-1. MS (EI) m/z (relative intensity) = 336 (16), 303(7), 276 (10), 263 (12), 245 (60), 191 (10), 137 (28). HRMS (FAB): m/z calcd for C₂₁H₃₆O₃Na: 359.2562; found: 359.2574.

Compound 31: ¹H NMR (400 MHz, CDCl₃): δ = 3.71 (s, 3 H), 2.13 (ddd, J = 14.0, 8.4, 4.6 Hz, 1 H), 1.85 (dt, J = 12.4, 3.3 Hz, 1 H), 1.79 (m, 2 H), 1.34 (s, 3 H), 1.22 (s, 3 H), 0.88 (dd, J = 12.5, 1.9 Hz, 1 H), 0.83 (s, 3 H), 0.76 (s, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 177.1 (C), 76.1 (C), 74.7 (C), 56.3 (CH), 52.4 (CH₃) 52.2 (CH), 42.7 (CH₂), 41.9 (CH₂), 39.0 (CH₂), 37.2 (C), 33.3 (CH₃), 33.2 (C), 31.3 (CH₂), 28.1 (CH₃), 25.6 (CH₃), 21.5 (CH₃), 19.9 (CH₂), 18.5 (CH₂), 15.0 (CH₃), 14.7 (CH₃). IR (film): 1738, 1461, 1378, 1283, 1103, 992, 892, 849, 760 cm^-1. MS (EI) m/z (relative intensity) = 323 (22), 307 (18), 263 (19), 245 (68), 196 (8), 137 (36). HRMS (FAB): m/z calcd for C₂₀H₃₄O₃Na: 345.2406; found: 345.2412.
Compound 35: ¹H NMR (400 MHz, CDCl₃): δ = 3.32 (d, J = 10.6 Hz, 1 H), 3.07 (d, J = 10.6 Hz, 1 H), 2.32 (s, 1 H), 1.29 (s, 3 H), 1.16 (s, 3 H), 1.10 (dd, J = 12.6, 2.4 Hz, 1 H), 0.99 (dd, J = 12.2, 1.5 Hz, 1 H), 0.85 (s, 3 H), 0.79 (s, 3 H), 0.76 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 75.5 (C), 73.3 (C), 70.9 (CH₂), 58.2 (CH), 56.4 (CH), 43.1 (CH₂), 42.2 (CH₂), 39.2 (CH₂), 36.9 (C), 33.4 (CH₃), 33.3 (C), 32.5 (CH₂), 25.1 (CH₃), 24.5 (CH₃), 21.3 (CH₃), 19.8 (CH₂), 18.6 (CH₂), 15.8 (CH₃), 15.0 (CH₃). IR (film): 3455, 1463, 1377, 1259, 1121, 1052, 960, 755 cm^-1. MS (EI) m/z (relative intensity) = 294 (8), 263 (14), 245 (76), 191 (10), 149 (12), 137 (40), 83 (71). HRMS (FAB): m/z calcd for C₁₉H₃₄O₂Na: 317.2456; found: 317.2448.