Synthesis of 3-Alkylseleno-2-cylcobutenone via [2+2] Cycloaddition Reaction of Alkyneselenolate with Diphenylketene

Abstract

3-Alkylseleno-2-cyclobutenones were synthesized by reaction of alkyneselenolate with diphenylketene via [2+2] cycloaddition. The complete structure of the 2-cyclobutenone was determined by X-ray diffraction.

[2+2] cycloaddition - 3-alkylseleno-2-cyclobutenone - alkyneselenolate - ketene - X-ray diffraction

References

<A NAME="RY02802ST-1A">1a</A> Allen AD. Cheng B. Fenwick MH. Givehchi B. Henry-Riyad H. Nikolaev VA. Shikhova EA. Tahmassebi D. Tidwell TT. Wang S. J. Org. Chem.  2001,  66:  2611 

<A NAME="RY02802ST-1B">1b</A> Zora M. Koyuncu I. Yucel B. Tetrahedron Lett.  2000,  41:  7111 

<A NAME="RY02802ST-1C">1c</A> Hergueta AR. Moore HW. J. Org. Chem.  1999,  64:  5979 

<A NAME="RY02802ST-1D">1d</A> Wipf P. Hopkins CR. J. Org. Chem.  1999,  64:  6881 

<A NAME="RY02802ST-1E">1e</A> Ohno M. Yamamoto Y. Eguchi S. Synlett  1998,  1167 

<A NAME="RY02802ST-1F">1f</A> Allen AD. Tidwell TT. Can. J. Chem.  1999,  77:  802 

<A NAME="RY02802ST-1G">1g</A> Paquette LA. Hamme ATII. Kuo LH. Doyon J. Kreuzholz R. J. Am. Chem. Soc.  1997,  119:  1242 

<A NAME="RY02802ST-1H">1h</A> Dillon JL. Gao Q. Dillon EA. Adams N. Tetrahedron Lett.  1997,  38:  2231 

<A NAME="RY02802ST-2A">2a</A> Dudley GB. Takaki KS. Cha DD. Danheiser RL. Org. Lett.  2000,  2:  3407 

<A NAME="RY02802ST-2B">2b</A> Zhang S. Liebeskind LS. J. Org. Chem.  1999,  64:  4042 

<A NAME="RY02802ST-2C">2c</A> MacDougall JM. Santora VJ. Verma SK. Turnbull P. Hernandez CR. Moore HW. J. Org. Chem.  1998,  63:  6905 

<A NAME="RY02802ST-3A">3a</A> Ikeda H. Kato T. Inagaki S. Chem. Lett.  2001,  270 

<A NAME="RY02802ST-3B">3b</A> Huang W. Fang D. Temple K. Tidwell TT. J. Am. Chem. Soc.  1997,  119:  2832 

<A NAME="RY02802ST-3C">3c</A> Niwayama S. Kallel EA. Sheu C. Houk KN. J. Org. Chem.  1996,  61:  2517 

<A NAME="RY02802ST-4A">4a</A> Koketsu M. Nada F. Ishihara H. Synthesis  2002,  195 

<A NAME="RY02802ST-4B">4b</A> Ishihara H. Koketsu M. Fukuta Y. Nada F. J. Am. Chem. Soc.  2001,  123:  8408 

<A NAME="RY02802ST-4C">4c</A> Koketsu M. Takenaka Y. Ishihara H. Synthesis  2001,  731 

<A NAME="RY02802ST-4D">4d</A> Koketsu M. Takenaka Y. Hiramatsu S. Ishihara H. Heterocycles  2001,  55:  1181 

<A NAME="RY02802ST-4E">4e</A> Koketsu M. Hiramatsu S. Ishihara H. Chem. Lett.  1999,  485 

<A NAME="RY02802ST-4F">4f</A> Koketsu M. Suzuki N. Ishihara H. J. Org. Chem.  1999,  64:  6473 

<A NAME="RY02802ST-4G">4g</A> Koketsu M. Senda T. Yoshimura K. Ishihara H. J. Chem. Soc., Perkin Trans. 1  1999,  453 

<A NAME="RY02802ST-5">5</A> Ishihara H. Yoshimi M. Kato S. Angew. Chem., Int. Ed. Engl.  1990,  29:  530 

<A NAME="RY02802ST-6A">6a</A> Koketsu M. Kanoh M. Itoh E. Ishihara H. J. Org. Chem.  2001,  66:  4099 

<A NAME="RY02802ST-6B">6b</A> Koketsu M. Yang HO. Kim YM. Ichihashi M. Ishihara H. Org. Lett.  2001,  3:  1705 

<A NAME="RY02802ST-6C">6c</A> Watanabe S. Mori E. Nagai H. Kataoka T. Synlett  2000,  49 

<A NAME="RY02802ST-6D">6d</A> Shimada K. Akimoto S. Itoh H. Nakamura H. Takikawa Y. Chem. Lett.  1994,  1743 

<A NAME="RY02802ST-7">7</A> Hyatt J. Raynolds PW. In Organic Reactions   Vol. 45:  Joyce RM. John Wiley & Sons, Inc.; New York: 1994.  p.159 

<A NAME="RY02802ST-8A">8a</A> Wasserman HH. Piper JU. Dehmlow EV. J. Org. Chem.  1973,  38:  1451 

<A NAME="RY02802ST-8B">8b</A> Wasserman HH. Dehmlow EV. Tetraherdon Lett.  1962,  1031 

<A NAME="RY02802ST-8C">8c</A> Barton DHR. Gardner JN. Petterson RC. Stamm OA. J. Chem. Soc.  1962,  2708 

<A NAME="RY02802ST-9">9</A>

This work was first reported at the 222nd National Meeting of the American Chemical Society, Chicago, August 26-30, 2001.

<A NAME="RY02802ST-10">10</A>

Procedure: 3-Methylseleno-2,4,4-triphenyl-2-cyclo-butenone 5a: Lithium alkyneselenolate 3 (2 equiv), generated in situ from phenylacetylene (2 equiv), n-BuLi
(2 equiv) and elementary selenium (2 equiv.), was added to THF solution of diphenylketene 2 which was generated from diphenylacetyl chloride 1 (1 equiv) and triethylamine (1 equiv) under argon atmosphere. Moreover, methyl iodide 4a (2 equiv) was added to the mixture and was stirred at room temperature for 1 h. The mixture was extracted with diethyl ether and washed with saturated NaCl solution. The organic layer was dried over sodium sulfate and evaporated to dryness. The residue was purified by flash chromatography on silica gel with n-hexane-diethyl ether (50:1) to give 0.20 g of 5a (51%) as pale yellow crystals; mp 120.9-122.3 °C; IR (KBr) 1734 cm^-1; ¹H NMR (CDCl₃) δ 2.12 (s, 3 H, CH₃), 7.27-7.47 (m, 13 H, Ar), 7.79 (d, J = 7.6 Hz, 2 H, Ar); ¹³C NMR (CDCl₃) δ 7.9, 81.7, 127.1, 127.5, 128.2, 128.5, 128.6, 128.8, 129.8, 138.7, 145.7, 169.2, 185.3; ⁷⁷Se NMR (CDCl₃) δ 257.8; MS (CI): m/z = 391 [M⁺ + 1]; Anal. Calcd for C₂₃H₁₈OSe: C, 70.95; H, 4.66. Found: C, 70.63; H, 4.66%. 3-Ethylseleno-2,4,4-triphenyl-2-cyclobutenone 5b: Pale yellow crystals; mp 111.4-113.2 °C; IR (KBr) 1741cm^-1; ¹H NMR (CDCl₃) δ 1.04 (t, J = 7.6 Hz, 3 H, CH₃), 2.86 (q, J = 7.6 Hz, 2 H, CH₂), 7.27-7.48 (m, 13 H, Ar), 7.80 (d, J = 7.6 Hz, 2 H, Ar); ¹³C NMR (CDCl₃) δ 14.7, 22.4, 81.6, 127.2, 127.5, 128.3, 128.5, 128.6, 129.9, 138.8, 145.2, 169.7, 185.4; ⁷⁷Se NMR (CDCl₃) δ 349.2; MS (CI): m/z = 405 [M⁺ + 1]; Anal. Calcd for C₂₄H₂₀OSe: C, 71.46; H, 5.00. found: C, 71.10; H, 5.01%.

<A NAME="RY02802ST-11A">11a</A> Wang KK. Chem. Rev.  1996,  96:  207 

<A NAME="RY02802ST-11B">11b</A> Sullivan RW. Coghlan VM. Munk SA. Reed MW. Moore HW. J. Org. Chem.  1994,  59:  2276 

<A NAME="RY02802ST-11C">11c</A> Nakatani K. Isoe S. Maekawa S. Saito I. Tetrahedron Lett.  1994,  35:  605 

<A NAME="RY02802ST-11D">11d</A> Liebeskind LS. Foster BS. J. Am. Chem. Soc.  1990,  112:  8612 

<A NAME="RY02802ST-11E">11e</A> Foland LD. Karlsson JO. Perris ST. Schwabe R. Xu SL. Patil S. Moore HW. J. Am. Chem. Soc.  1989,  111:  975 

<A NAME="RY02802ST-12A">12a</A> Dudley GB. Takaki KS. Cha DD. Danheiser RL. Org. Lett.  2000,  2:  3407 

<A NAME="RY02802ST-12B">12b</A> Loebach JL. Bennett DM. Danheiser RL. J. Org. Chem.  1998,  63:  8380 

<A NAME="RY02802ST-13">13</A> Danheiser RL. Sard H. Tetrahedron Lett.  1983,  24:  23 

<A NAME="RY02802ST-14">14</A>

Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication, CCDC No. 176955 for 5b. Copies of this information can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax:[phone] or e-mail: [e-mail]).

<A NAME="RY02802ST-15">15</A> Ishihara H. Yoshimi M. Hara N. Ando H. Kato S. Bull. Chem. Soc. Jpn.  1990,  63:  835 

<A NAME="RY02802ST-16A">16a</A> Kowalski CJ. Haque MSJ. J. Am. Chem. Soc.  1986,  108:  1325 

<A NAME="RY02802ST-16B">16b</A> Kowalski CJ. Fields KW. J. Am. Chem. Soc.  1978,  104:  321 

<A NAME="RY02802ST-16C">16c</A> Miyaura N. Yanagi T. Suzuki A. Chem. Lett.  1979,  535 

<A NAME="RY02802ST-16D">16d</A> Schöllkopf VU. Hoppe I. Angew. Chem.  1975,  87:  814 

<A NAME="RY02802ST-17A">17a</A> Zaitseva GS. Livantsova LI. Baukov YI. Lutsenko IF. Zh. Obshch. Khim.  1984,  54:  1323 ; Chem. Abstr. 1984, 101, 171389s

<A NAME="RY02802ST-17B">17b</A> Hong P. Sonogashira K. Hagihara N. J. Organomet. Chem.  1981,  219:  363 

<A NAME="RY02802ST-18A">18a</A> Miller R. Claudio A. Adel S. In Ulmann’s Encyclopedia of Industrial Chemistry   Vol. A15:  Elvers B. Hawkins S. Schulz G. VCH Verlagasgesellschaft; Weinheim Germany: 1990.  p.63 

<A NAME="RY02802ST-18B">18b</A> Seikaly HR. Tidwell TT. Tetrahedron  1986,  42:  2587 

<A NAME="RY02802ST-18C">18c</A> Ulrich H. Cycloaddition Reactions of Heterocummulenes   Academic Press; New York: 1967. 

<A NAME="RY02802ST-18D">18d</A> Quadbeck G. Angew. Chem.  1956,  68:  361