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Synlett 2003(5): 0655-0658
DOI: 10.1055/s-2003-38359
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

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)

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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.