A New Synthesis of α-Phenylseleno γ- and δ-Lactones from Terminal Alkynes

Marcello Tiecco; Lorenzo Testaferri; Andrea Temperini; Luana Bagnoli; Francesca Marini; Claudio Santi

doi:10.1055/s-2003-38359

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Synlett 2003(5): 0655-0658
DOI: 10.1055/s-2003-38359

LETTER

A New Synthesis of α-Phenylseleno γ- and δ-Lactones from Terminal Alkynes

Marcello Tiecco*, Lorenzo Testaferri, Andrea Temperini, Luana Bagnoli, Francesca Marini, Claudio Santi
Dipartimento di Chimica e Tecnologia del Farmaco, Sezione di Chimica Organica, Università degli Studi di Perugia, 06123 Perugia, Italy
Fax: +39(75)5855116; e-Mail: tiecco@unipg.it;

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Publication History

Received 15 January 2003
Publication Date:
28 March 2003 (online)

Abstract
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Abstract

Treatment of the hydroxy substituted (Z)-a-(phenylseleno)vinyl p-toluenesulfonates with electrophilic phenylselenenylating agents gives rise to a selenium induced ring closure reaction affording a-phenylseleno g- or d-lactones.

Key words

selenium - electrophilic additions - cyclization reactions - lactones

References

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17

All new compounds were fully characterized by MS, ¹H and ¹³C NMR spectroscopy and by combustion analysis. Compounds 8b, [21] 8c and 8d [22] were obtained by the previously described procedure. Compound 8f was prepared by reduction of the corresponding ketone [23] with NaBH₄. The acetoxy derivatives 9 of 2- or 3-alkynyl alcohols were obtained after treatment with AcCl in a solution of pyridine/CH₂Cl₂ 1:3 at 0 °C. The alkynyl phenyl selenides 10 and the α-(phenylseleno)vinyl p-toluenesulfonates 11 were prepared as previously described.¹⁶ Physical, spectral and analytical data of some selected compounds are reported below. Oct-7-yn-4-ol ( 8f) (81% yield): Oil. ¹H NMR: δ = 3.83-3.62 (m, 1 H), 2.47-2.18 (m, 3 H), 1.98 (t, 1 H, J = 2.7 Hz), 1.74-1.20 (m, 6 H), 0.92 (t, 3 H, J = 7.3 Hz). ¹³C NMR: δ = 84.3, 70.3, 68.5, 39.5, 35.7, 18.7, 14.9, 13.9. MS: m/z (relative intensity) = 126 (3), 83 (94), 73 (45), 55 (100), 43 (55). Anal. Calcd for C₈H₁₄O: C, 76.14; H, 11.18. Found: C, 76.30; H, 11.10.
1-(Butoxymethyl)but-3-ynyl acetate ( 9d) (88% yield): Oil. ¹H NMR: δ = 5.05 (ddt, 1 H, J = 6.4, 6.0 and 5.0 Hz), 3.59 (d, 2 H, J = 5.0 Hz), 3.51 (dt, 1 H, J = 9.4 and 6.3 Hz), 3.44 (dt, 1 H, J = 9.4 and 6.5 Hz), 2.6 (ddd, 1 H, J = 16.9, 6.4 and 2.7 Hz), 2.48 (ddd, 1 H, J = 16.9, 6.0 and 2.7 Hz), 2.08 (s, 3 H), 2.03 (t, 1 H, J = 2.7 Hz), 1.64-1.44 (m, 2 H), 1.44-1.24 (m, 2 H), 0.92 (t, 3 H, J = 7.2 Hz). ¹³C NMR: δ = 169.9, 79.2, 71.1, 70.3, 70.0 (2 C), 31.4, 20.6 (2 C), 19.0, 13.6. MS: m/z (relative intensity): 198 (1), 81 (32), 57 (77), 43 (100). Anal. Calcd for C₁₁H₁₈O₃: C, 66.64; H, 9.15. Found: C, 66.57; H, 9.10.
1-(Butoxymethyl)-4-(phenylseleno)but-3-ynyl acetate ( 10d) (88% yield): Oil. ¹H NMR: δ = 7.54-7.42 (m, 2 H), 7.34-7.20 (m, 3 H), 5.11 (ddt, 1 H, J = 6.3, 5.9 and 4.9 Hz), 3.61 (d, 2 H, J = 4.9 Hz), 3.48 (dt, 1 H, J = 9.3 and 6.3 Hz), 3.42 (dt, 1 H, J = 9.3 and 6.4 Hz), 2.87 (dd, 1 H, J = 17.0 and 6.3 Hz), 2.77 (dd, 1 H, J = 17.0 and 5.9 Hz), 2.06 (s, 3 H), 1.62-1.46 (m, 2 H), 1.46-1.32 (m, 2 H), 0.91 (t, 3 H, J = 7.2 Hz). ¹³C NMR: δ = 170.2, 129.3 (2 C), 128.7 (3 C), 126.8, 99.1, 71.3, 70.6, 70.3, 70.2, 31.5, 22.7, 21.0, 19.1, 13.7. MS: m/z (relative intensity): 354 (4), 237 (17), 157 (38), 141 (53), 115 (46), 81 (43), 57 (32), 43 (100). Anal. Calcd for C₁₇H₂₂O₃Se: C, 57.80; H 6.28. Found: C, 57.85; H, 6.34.
Trans-2-[( Z )-2-{[(4-Methylphenyl)sulfonyl]oxy}-2-(phenylseleno)ethenyl]cyclohexyl acetate ( 11b) (72% yield): Oil. ¹H NMR: δ = 7.68-7.58 (m, 2 H), 7.42-7.30 (m, 2 H), 7.20-7.12 (m, 5 H), 5.62 (d, 1 H, J = 9.9 Hz), 4.55 (dt, 1 H, J = 10.2 and 4.4 Hz), 2.75-2.48 (m, 1 H), 2.41 (s, 3 H), 2.01 (s, 3 H), 1.82-1.54 (m, 2 H), 1.44-1.08 (m, 6 H). ¹³C NMR: δ = 170.0, 144.9, 138.8, 134.3, 132.5, 129.4 (3 C), 129.0 (2 C), 128.3 (3 C), 127.5 (2 C), 74.7, 44.7, 31.2, 31.1, 24.4, 24.1, 21.5, 21.1. Anal. Calcd for C₂₃H₂₆O₅SSe: C, 55.99; H, 5.31. Found: C, 55.95; H, 5.27.
3-( Z )-1-(Butoxymethyl)-4-{[(4-methylphenyl)sulfon-yl]oxy}-4-(phenylseleno)but-3-enyl acetate ( 11d) (56% yield): Oil. ¹H NMR: δ = 7.72-7.62 (m, 2 H), 7.40-7.14 (m, 7 H), 5.95 (t, 1 H, J = 7.7 Hz), 4.99 (dt, 1 H, J = 6.2 and 5.5 Hz), 3.54-3.40 (m, 4 H), 2.60 (dd, 2 H, J = 7.7 and 6.2 Hz), 2.42 (s, 3 H), 2.04 (s, 3 H), 1.62-1.20 (m, 4 H), 0.96 (t, 3 H, J = 7.2 Hz). ¹³C NMR: δ = 170.2, 145.1, 140.1, 132.3 (2 C), 130.2, 129.5 (3 C), 129.1 (2 C), 128.4 (3 C), 127.6, 71.2 (2 C), 70.8, 31.8, 31.6, 21.6, 21.0, 19.2, 13.8. Anal. Calcd for C₂₄H₃₀O₆SSe: C, 54.85; H, 5.75. Found: C, 55.05; H, 5.70.
4-( Z )-5-{[(4-Methylphenyl)sulfonyl]oxy}-5-(phenyl-seleno)-1-propylpent-4-enyl acetate ( 11f) (80% yield): Oil. ¹H NMR: δ = 7.75-7.62 (m, 2 H), 7.43-7.12 (m, 7 H), 5.96 (t, 1 H, J = 7.5 Hz), 4.90-4.32 (m, 1 H), 2.42 (s, 3 H), 2.21 (q, 2 H, J = 7.5 Hz), 2.00 (s, 3 H), 1.68-1.10 (m, 6 H), 0.88 (t, 3 H, J = 7.1 Hz). ¹³C NMR: δ = 170.6, 145.0, 138.1, 133.2, 131.9 (2 C), 129.8 (2 C), 129.4 (2 C), 129.1 (2 C), 128.4, 127.3 (2 C), 73.1, 35.9, 32.9, 26.0, 21.5, 21.0, 18.3, 13.7. Anal. Calcd for C₂₃H₂₈O₅SSe: C, 55.76; H, 5.70. Found: C, 55.80; H, 5.76.

19

Ring Closure Reaction. General Procedure. To a solution of the acetoxy (Z)-α-(phenylseleno)vinyl p-toluene-sulfonate(11) (1 mmol) in methanol (8 mL), powdered potassium hydroxide (1 mmol) was added at r.t. When the starting material disappeared the solution was evaporated and the residue extracted with Et₂O, dried (Na₂SO₄) and concentrated in vacuo. Diphenyl diselenide (0.6 mmol) and DDQ (0.6 mmol) were added to a mixture of 5 (1 mmol) in MeCN and stirred at 30 °C. The progress of the reaction was monitored by TLC. Reaction times ranged from 24 h to 36 h. The reaction mixture was poured into 10% Na₂CO₃ solution to eliminate the formed hydroquinone and extracted with Et₂O. The organic layer was dried (Na₂SO₄) and evaporated. After column chromatography, compounds 6 and 7 were obtained in a pure form. Compounds 6a ⁹ and 7a ⁸ have physical and spectral data identical to those reported in the literature. The geometry of the two isomers of compounds 6c and 6d were tentatively assigned on the basis of the NMR data reported in the literature [12] for compounds having very similar structures. Physical and spectral data of 6c, 6d and of other compounds are reported below.
3a( R , S )-7a( R , S )-3-(Phenylseleno)hexahydro-1-benzo-furan-2(3 H )-one ( 6b) (73% yield): Oil. ¹H NMR: δ = 7.74-7.54 (m, 2 H), 7.42-7.16 (m, 3 H), 3.90-3.60 (m, 2 H), 2.34-2.08 (m, 1 H), 2.06-1.62 (m, 4 H), 1.60-1.08 (m, 4 H). ¹³C NMR: δ = 174.7, 135.5 (2 C), 129.4, 129.1 (2 C), 128.5, 83.3, 50.6, 45.2, 30.1, 27.2, 25.0, 24.0. MS: m/z (relative intensity): 298 (18), 157 (28), 129 (21), 95 (100), 91 (24), 67 (47), 55 (31), 41 (29). Anal. Calcd for C₁₄H₁₆O₂Se: C, 59.97; H, 5.46. Found: C, 60.02; H, 5.51.
5-Decyl-3-(phenylseleno)dihydrofuran-2(3 H )-one ( 6c) (67% yield): trans-Diastereoisomer: ¹H NMR: δ = 7.76-7.62 (m, 2 H), 7.44-7.20 (m, 3 H), 4.42-4.32 (m, 1 H), 4.02-3.88 (m, 1 H), 3.72-3.56 (m, 1 H), 2.42-2.24 (m, 2 H), 2.06-1.90 (m, 1 H), 1.78-1.08 (m, 16 H), 0.88 (t, 3 H, J = 6.5 Hz). ¹³C NMR: δ = 178.7, 135.6 (2 C), 129.3 (2 C), 129.0, 128.8, 79.3, 37.1, 36.7, 35.2, 31.8, 29.4 (4 C), 29.2, 25.0, 22.6, 14.0. cis-Diastereoisomer: ¹H NMR: δ = 7.72-7.60 (m, 2 H), 7.42-7.24 (m, 3 H), 4.46-4.30 (m, 1 H), 4.02 (t, 1 H, J = 9.4 Hz), 3.44-3.24 (m, 1 H), 2.72 (ddd, 1 H, J = 13.4, 9.4 and 6.6 Hz), 1.94 (ddd, 1 H, J = 13.4, 9.4 and 8.6 Hz), 1.68-1.10 (m, 17 H), 0.89 (t, 3 H, J = 6.7 Hz). ¹³C NMR: δ = 175.6, 135.5 (2 C), 129.2 (2 C), 128.7, 128.0, 79.2, 37.5, 36.0, 35.4, 31.8, 29.4, 29.3 (3 C), 29.2, 24.9, 22.6, 14. Anal. Calcd for C₂₀H₃₀O₂Se: C, 62.99; H, 7.93. Found: C, 62.92; H, 7.88.
5-(Butoxymethyl)-3-(phenylseleno)dihydrofuran-2(3 H )-one ( 6d) (76% yield): Oil. trans-Diastereoisomer: ¹H NMR: δ = 7.70-7.58 (m, 2 H), 7.44-7.18 (m, 3 H), 4.43 (ddt, 1 H, J = 7.3, 6.5 and 3.8 Hz), 4.05 (dd, 1 H, J = 8.9 and 5.2 Hz), 3.68-3.24 (m, 4 H), 2.59 (ddd, 1 H, J = 13.8, 8.9 and 6.5 Hz), 2.28 (ddd, 1 H, J = 13.8, 7.3 and 5.2 Hz), 1.64-1.12 (m, 4 H), 0.89 (t, 3 H, J = 7.2 Hz). ¹³C NMR: δ = 175.6, 135.5 (2 C), 129.2 (2 C), 128.8, 128.4, 77.6, 71.5 (2 C), 36.8, 32.5, 31.5, 19.1, 13.7. MS: m/z (relative intensity) = 328 (62), 183 (32), 157 (62), 116 (67), 77 (33), 57 (100), 41(34). cis-Diastereo-isomer: ¹H NMR: δ = 7.76-7.58 (m, 2 H), 7.44-7.16 (m, 3 H), 4.55 (ddt, 1 H, J = 7.5, 7.3 and 4.7 Hz), 3.98 (dd, 1 H, J = 9.8 and 8.5 Hz), 3.43 (t, 2 H, J = 4.6 Hz), 3.42 (t, 2 H, J = 4.7 Hz), 2.72 (ddd, 1 H, J = 13.7, 9.8 and 7.3 Hz), 2.18 (ddd, 1 H, J = 13.7, 8.5 and 7.5 Hz), 1.64-1.14 (m, 4 H), 0.91 (t, 3 H, J = 7.2 Hz). ¹³C NMR: δ = 175.0, 135.3 (2 C), 129.2 (2 C), 128.6, 128.3, 77.5, 71.6 (2 C), 36.9, 32.2, 31.5, 19.1, 13.8. MS: m/z (relative intensity) = 328 (38), 183 (14), 157 (34), 115 (25), 97 (25), 77 (20), 57 (100), 41 (24). Anal. Calcd for C₁₅H₂₀O₃Se: C, 55.06; H, 6.16. Found: C, 55.10; H, 6.19.
3-(Phenylseleno)-6-propyltetrahydro-2 H -pyran-2-one ( 7b) (40% yield): Mixture of two diastereoisomers (1:1). Oil. ¹H NMR: δ = 7.72-7.54 (m, 4 H), 7.42-7.18 (m, 6 H), 4.42-4.20 (m, 2 H), 4.10-3.85 (m, 2 H), 2.40-1.15 (m, 16 H), 1.10-0.78 (m, 6 H). ¹³C NMR: δ = 170.6 (2 C), 135.4 (4 C), 129.7, 129.1 (4 C), 128.5 (2 C), 127.8, 80.6, 79.5, 39.6, 37.8, 37.7 (2 C), 27.5, 26.9, 26.6, 25.8, 17.9 (2 C), 13.6 (2 C). MS: m/z (relative intensity) = 298 (100), 184 (87), 157 (60), 104 (34), 78 (33), 55 (70), 41 (48). Anal. Calcd for C₁₄H₁₈O₂Se: C, 56.58; H, 6.10. Found: C, 56.52; H, 6.04.