Organosulfur- or Organoselenium-Induced Intramolecular Cycloaddition of β-Allenic  α-Difluoromethylenephosphonic  Acid  Monoesters:  Synthesis of Novel Cyclic Phosphate Mimics

Yun Lin; Jin-Tao Liu

doi:10.1055/s-2006-948204

LETTER

Organosulfur- or Organoselenium-Induced Intramolecular Cycloaddition of β-Allenic α-Difluoromethylenephosphonic Acid Monoesters: Synthesis of Novel Cyclic Phosphate Mimics

Yun Lin^a,b, Jin-Tao Liu*^a
^a Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, P. R. of China
^b College of Chemistry and Environment Science, Nanjing Normal University, 122 Ninghai Road, Nanjing 210097, P. R. of China
Fax: +86(21)64166128; e-Mail: jtliu@mail.sioc.ac.cn;

Abstract

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Abstract

Novel cyclic phosphate mimics, γ-organosulfur or organoselenium substituted α-difluoromethylenephostones were synthesized in good yields with high regioselectivity under mild conditions by the electrophilic cyclization of β-allenic α-difluoromethylenephosphonic acid monoesters induced by ArSCl or ArSeCl. The reaction represents the first example of an intramolecular addition of phosphonic acid monoesters to β-allenic carbon-carbon double bonds.

Key words

β-allenic α-difluoromethylenephosphonic acid monoester - phosphate mimic - α-difluoromethylenephostone - organoselenium - organosulfur - cyclization

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<A NAME="RW09006ST-1A">1a</A> Blackburn GM. Brown D. Martin SJ. Parratt MJ. J. Chem. Soc., Perkin Trans. 1 1987, 181

<A NAME="RW09006ST-1B">1b</A> Blackburn GM. Kent DE. J. Chem. Soc., Perkin Trans. 1 1986, 913

<A NAME="RW09006ST-1C">1c</A> Blackburn GM. Brown D. Martin SJ. J. Chem. Res., Synop. 1985, 92

<A NAME="RW09006ST-1D">1d</A> Blackburn GM. England DA. Kolkman FJ. J. Chem. Soc., Chem. Commun. 1981, 930

<A NAME="RW09006ST-2A">2a</A> Eggenspiller A. Berges-Gross V. Danzin C. Tetrahedron 1996, 52: 177

<A NAME="RW09006ST-2B">2b</A> Kawamoto AM. Campbell MM. J. Chem. Soc., Perkin Trans. 1 1997, 1249

<A NAME="RW09006ST-2C">2c</A> Caplan NA. Pogson CI. Hayes DJ. Blackburn GM. J. Chem. Soc., Perkin Trans. 1 2000, 3: 421

<A NAME="RW09006ST-2D">2d</A> Yokomatsu T. Hayakawa Y. Kihara T. Koyanagi S. Soeda S. Shimeno H. Shibuya S. Bioorg. Med. Chem. 2000, 8: 2571

<A NAME="RW09006ST-2E">2e</A> Xu Y. Prestwich GD. Org. Lett. 2002, 4: 4021

<A NAME="RW09006ST-2F">2f</A> Hum G. Lee J. Taylor SD. Bioorg. Med. Chem. Lett. 2002, 12: 3471

<A NAME="RW09006ST-2G">2g</A> Pfund E. Lequeux T. Masson S. Vazeux M. Org. Lett. 2002, 4: 843

<A NAME="RW09006ST-2H">2h</A> Yokomatsu T. Kato J. Sakuma C. Shibuya S. Synlett 2003, 1407

<A NAME="RW09006ST-2I">2i</A> Murano T. Yuasa Y. Kobayakawa H. Yokomatsu T. Shibuya S. Tetrahedron 2003, 59: 10223

<A NAME="RW09006ST-2J">2j</A> Li XF. Bhandari A. Holmes CP. Szardenings AK. Bioorg. Med. Chem. Lett. 2004, 14: 4301

<A NAME="RW09006ST-2K">2k</A> Gautier A. Garipova G. Salcedo C. Balieu S. Piettre SR. Angew. Chem. Int. Ed. 2004, 43: 5963

<A NAME="RW09006ST-3A">3a</A> Thatcher GR. Campbell AS. J. Org. Chem. 1993, 58: 2272

<A NAME="RW09006ST-3B">3b</A> Berkowitz DB. Eggen M. Shen QR. Shoemaker RK. J. Org. Chem. 1996, 61: 4666

<A NAME="RW09006ST-3C">3c</A> Butt AH. Percy JM. Spencer N. Chem. Commun. 2000, 1691

<A NAME="RW09006ST-3D">3d</A> Marano T. Yuasa Y. Kobayakawa H. Yokomatsu T. Shibuya S. Tetrahedron 2003, 59: 10223

<A NAME="RW09006ST-4">4</A> Lloir LF. Biochem. Biophys. 1951, 33: 186

<A NAME="RW09006ST-5">5</A> Markham R. Smith JD. Biochem. J. 1952, 52: 552

<A NAME="RW09006ST-6">6</A> Forrest HS. Todd AR. J. Chem. Soc. 1950, 3295

<A NAME="RW09006ST-7">7</A> Dawson RM. Freinkel N. Jungalwala FB. Clarke N. Biochem. J. 1971, 122: 605

<A NAME="RW09006ST-8">8</A> Shinitzky M. Friedman P. Haimovitz R. J. Biol. Chem. 1993, 268: 14109

<A NAME="RW09006ST-9">9</A> Friedman P. Haimovitz R. Markman O. Roberts MF. Shinitzky M. J. Biol. Chem. 1996, 271: 953

For recent references, see:

<A NAME="RW09006ST-10A">10a</A> Meier C. Lorey M. Clercq ED. Balzarini J. Bioorg. Med. Chem. Lett. 1997, 7: 99

<A NAME="RW09006ST-10B">10b</A> Gypakis A. Wasner HK. Biol. Chem. 2000, 381: 1139

<A NAME="RW09006ST-10C">10c</A> Kaur K. Lan MJK. Pratt RF. J. Am. Chem. Soc. 2001, 123: 10436

<A NAME="RW09006ST-10D">10d</A> Liu Y. Bruzik KS. Ananthanarayanan B. Cho W. Bioorg. Med. Chem. 2003, 11: 2471

<A NAME="RW09006ST-10E">10e</A> Wang P. Wu P. Egan RW. Billah MM. Gene 2003, 314: 15

<A NAME="RW09006ST-10F">10f</A> Fujiwara Y. Seboek A. Meakin S. Kobayashi T. J. Neurochem. 2003, 87: 1272

<A NAME="RW09006ST-10G">10g</A> Pelash A. Shinitzky M. Biochem. Biophys. Res. Commun. 2004, 315: 1045

<A NAME="RW09006ST-11">11</A> Frederickson M. Grigg R. Org. Prep. Proced. Int. 1997, 29: 33

<A NAME="RW09006ST-12A">12a</A> Ihara M. Hags Y. Yonekura M. Ohsawa T. Fukumoto K. J. Am. Chem. Soc. 1983, 105: 7345

<A NAME="RW09006ST-12B">12b</A> Mühlstädt M. Schubert C. Kleinpeter E. J. Prakt. Chem. 1985, 2: 270

<A NAME="RW09006ST-12C">12c</A> Berthe B. Outurquin F. Paulmier C. Tetrahedron Lett. 1997, 38: 1393

<A NAME="RW09006ST-12D">12d</A> Brugier D. Outurquin M. Paulmier C. J. Chem. Soc., Perkin Trans. 1 2001, 1: 37

<A NAME="RW09006ST-12E">12e</A> Jana G. Viso A. Diaz Y. Castillon S. Eur. J. Org. Chem. 2003, 209

<A NAME="RW09006ST-12F">12f</A> Bugarcic ZM. Gavrilovic M. Monatsh. Chem. 2003, 134: 1359

<A NAME="RW09006ST-12G">12g</A> Marshall J. Wang X. J. Org. Chem. 1990, 55: 2995

<A NAME="RW09006ST-12H">12h</A> Ma S. Pan F. Hao X. Huang X. Synlett 2004, 85

<A NAME="RW09006ST-12I">12i</A> Enchev DD. Heteroat. Chem. 2005, 16: 156

<A NAME="RW09006ST-13A">13a</A> Paulmier C. Selenium Reagents and Intermediates in Organic Synthesis Pergamon; Oxford: 1986.

<A NAME="RW09006ST-13B">13b</A> Organoselenium Chemistry: A Practical Approach Back TG. Oxford University; Oxford: 1999.

<A NAME="RW09006ST-13C">13c</A> Organoselenium Chemistry: Modern Developments in Organic Synthesis Wirth T. Springer; Berlin: 2000.

<A NAME="RW09006ST-13D">13d</A> Oae S. Organic Chemistry of Sulfur: Structure and Mechanism CRC; London: 1991.

<A NAME="RW09006ST-13E">13e</A> Glass RS. Top. Curr. Chem. 1999, 205: 2

Cyclic Products 2 or 3; Typical Procedure: To a solution of 1 (0.5 mmol) in MeCN (6 mL) in a dry Schlenk tube was slowly added p-MeC₆H₄SCl or PhSeCl (0.75 mmol) in MeCN (2 mL) at -30 °C under a N₂ atmosphere. After the reaction was complete (monitored by TLC, ca. 30 min), the reaction mixture was concentrated and the residue was purified by flash chromatography on silica gel to give product 2 or 3.
Compound 2a Mp 54-55 °C. IR (KBr): 1616, 1285, 1116, 1037, 1005 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.40-7.38 (m, 2 H), 7.28-7.25 (m, 2 H), 5.05-4.92 (m, 1 H), 4.35-4.29 (m, 2 H), 2.40 (s, 3 H), 1.85 (s, 3 H), 1.74 (s, 3 H), 1.38 (t, J = 6.6 Hz, 3 H). ¹⁹F NMR (282 MHz, CDCl₃): δ = -101.08 (AB, dd, J _F-F = 308.7 Hz, J _P-F = 95.6 Hz, J _H-F = 11.6, 10.1, 7.9 Hz). ³¹P NMR (121 MHz, CDCl₃): δ = -0.58 to -2.54 (m). EIMS: m/z (%) = 348 (M⁺, 29.56), 225 (35.63), 189 (100.00), 117 (56.26), 107 (27.57), 97 (56.06), 77 (58.91). Anal. Calcd for C₁₅H₁₉F₂O₃PS: C, 51.72; H, 5.50. Found: C, 51.92; H, 5.49.
Compound 3a Mp 56-57 °C. IR (KBr): 1621, 1285, 1027, 1001 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 7.64-7.61 (m, 2 H), 7.49-7.28 (m, 3 H), 5.41-5.29 (m, 1 H), 4.37-4.32 (m, 2 H), 1.85 (s, 3 H), 1.75 (s, 3 H), 1.40 (t, J = 7.2 Hz, 3 H). ¹⁹F NMR (282 MHz, CDCl₃): δ = -102.16 (AB, dd, J _F-F = 311.8 Hz, J _P-F = 95.6 Hz, J _H-F = 10.2, 8.5, 7.9 Hz). ³¹P NMR (121 MHz, CDCl₃): δ = -0.71 to -2.64 (m). EIMS: m/z (%) = 382 (M⁺, 2.47), 381 (14.23), 223 (17.00), 133 (10.31), 117 (100.00), 97 (35.47), 77 (50.49), 65 (10.49), 51 (18.10). Anal. Calcd for C₁₄H₁₇F₂O₃PSe: C, 44.11; H, 4.49. Found: C, 44.12; H, 4.60.