Download PDF
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;
Further Information

Publication History

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

    Permissions and Reprints All articles of this category

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

  • 1 Topics in Current Chemistry: Organoselenium Chemistry, Modern Developments in Organic Synthesis; Wirth T. Ed. Springer; Berlin: 2000. 
  • 2 Organoselenium Chemistry - A Practical Approach   Back TG. Oxford; New York: 2000. 
  • 3 Liotta D. Organoselenium Chemistry   Wiley; New York: 1987. 
  • 4 Paulmier C. Selenium Reagents and Intermediates in Organic Synthesis   Pergamon Press; Oxford: 1986. 
  • 5 Sharpless KB. Lauer RF. Teranishi AY. J. Am. Chem. Soc.  1973,  95:  6137 
    CrossrefSearch in Google Scholar
  • 6 Reich HJ. Renga JM. Reich IL. J. Am. Chem. Soc.  1975,  97:  5432 
    Search in Google Scholar
  • 7 Nicolaou KC. Petatis NA. Selenium in Natural Products Synthesis   CIS; Philadelphia: 1984. 
  • 8 Krief A. Lucchetti J. Tetrahedron Lett.  1978,  30:  2693 
    Search in Google Scholar
  • 9 Detty MR. Wood GP. J. Org. Chem.  1980,  45:  80 
    CrossrefSearch in Google Scholar
  • 10 Grieco PA. Miyashita M. J. Org. Chem.  1974,  39:  120 
    Search in Google Scholar
  • 11 Hanessian S. Hodges PJ. Murray PJ. Sahoo SP. J. Chem. Soc., Chem. Commun.  1986,  754 
  • 12 Figuredo M. Font J. Virgili A. Tetrahedron  1987,  43:  1881 
    CrossrefSearch in Google Scholar
  • 13 Silveira CC. Araujo MA. Lenardao EJ. Braga AL. Dabdoub MJ. Synthesis  1995,  1305 
    Thieme Connect
  • 14 Tiecco M. Electrophilic Selenium, Selenocyclizations, In Topics in Current Chemistry: Organoselenium Chemistry   Wirth T. Springer; Berlin: 2000. 
  • 15 Tingoli M. Tiecco M. Testaferri L. Temperini A. Pelizzi G. Bacchi A. Tetrahedron  1995,  51:  4691 
    CrossrefSearch in Google Scholar
  • 16 Tiecco M. Testaferri L. Temperini A. Bagnoli L. Marini F. Santi C. Synlett  2001,  706 
  • 18 Tiecco M. Testaferri L. Temperini A. Bagnoli L. Marini F. Santi C. Synlett  2001,  1767 
    Thieme Connect
  • 20a Wilson LJ. Liotta D. Tetrahedron Lett.  1990,  31:  1815 
    CrossrefSearch in Google Scholar
  • 20b Wang J. Wurster JA. Wilson LJ. Liotta D. Tetrahedron Lett.  1993,  34:  4881 
    CrossrefSearch in Google Scholar
  • 20c Chu CK. Rameshbabu T. Warren Beach J. Ahn SH. Huang H. Jeong LS. Lee SJ. J. Org. Chem.  1990,  55:  1418 
    CrossrefSearch in Google Scholar
  • 20d Diaz V. El-Laghdach A. Matheu MI. Castillon S. J. Org. Chem.  1997,  62:  1501 
    CrossrefSearch in Google Scholar
  • 21 Carlson RG. Henton DE. J. Chem. Soc., Chem. Commun.  1969,  674 
  • 22 Tikhvinskaya MY. Berdnikov AE. Kankina AK. Vlasov VM. Uch. Zap. Yarosl. Gos. Pedagog. Inst.  1973,  122:  54 ; Chem Abstr. 1975, 82, 169932j
    Search in Google Scholar
  • 23 Schultze KE. Reisch J. Bergental D. Chem. Ber.  1968,  101:  1540 
    Search in Google Scholar
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.