Copper-Catalyzed Addition of Halide and Sulfide Groups to Alkynes Utilizing Disulfides with Tetrabutylammonium Halides

Abstract

A copper-catalyzed addition of halide and sulfide groups to internal alkynes was carried out using disulfides with n-Bu₄NX (X = Br, I or Cl) in air. The present reaction can selectively prepare the corresponding anti-configured haloalkenyl sulfide, and uses both sulfide groups of the disulfide reagent.

alkenyl sulfides - alkenyl halides - copper catalyst - di­sulfides - internal alkynes

References and Notes

<A NAME="RU12007ST-1A">1a</A> Ley SV. Thomas AW. Angew. Chem. Int. Ed.  2003,  42:  5400 

<A NAME="RU12007ST-1B">1b</A> Kondo T. Mitsudo T. Chem. Rev.  2000,  100:  3205 

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<A NAME="RU12007ST-2A">2a</A> Kuniyasu H. Ogawa A. Sato K.-I. Ryu I. Kambe N. Sonoda N. J. Am. Chem. Soc.  1992,  114:  5902 

<A NAME="RU12007ST-2B">2b</A> Ananikov VP. Kabeshov MA. Beletskaya IP. Khrustalev VN. Antipin MY. Organometallics  2005,  24:  1275 

<A NAME="RU12007ST-2C">2c</A> Ogawa A. Kuniyasu H. Sonoda N. Hirao T. J. Org. Chem.  1997,  62:  8361 

<A NAME="RU12007ST-2D">2d</A> Bäckvall J.-E. Ericsson A. J. Org. Chem.  1994,  59:  5850 

<A NAME="RU12007ST-2E">2e</A> Kuniyasu H. Ogawa A. Miyazaki S.-I. Ryu I. Kambe N. Sonoda N. J. Am. Chem. Soc.  1991,  113:  9796 

<A NAME="RU12007ST-3A">3a</A> Ogawa A. Ikeda T. Kimura K. Hirao T. J. Am. Chem. Soc.  1999,  121:  5108 

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<A NAME="RU12007ST-5A">5a</A> Okuyama T. Izawa K. Fueno T. J. Org. Chem.  1974,  39:  351 

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<A NAME="RU12007ST-6">6</A> Taniguchi N. J. Org. Chem.  2006,  71:  7874 

<A NAME="RU12007ST-7">7</A>

Typical Procedure: To a mixture of CuI (1.9 mg, 0.01 mmol), bpy (1.6 mg, 0.01 mmol), diphenyl disulfide (21.8 mg, 0.1 mmol), and TBAB (70.9 mg, 0.22 mmol) in AcOH (0.3 mL) was added 4-octyne (22.0 mg, 0.2 mmol), and the mixture was stirred at 100 °C for 18 h in air. After the residue was dissolved in Et₂O, the solution was washed with H₂O and sat. NaCl and dried over anhyd MgSO₄. Chromatography on silica gel(hexane) gave (E)-4-bromo-5-phenylthiooctene (48.7 mg, 81%).
( E )- n -Pr(PhS)C=C(Br) n -Pr: IR (neat): 2960, 2870, 1582, 1476, 1461 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.16-7.31 (m, 5 H), 2.90 (t, J = 7.5 Hz, 2 H), 2.38 (t, J = 7.5 Hz, 2 H), 1.51-1.67 (m, 4 H), 0.92 (t, J = 7.5 Hz, 3 H), 0.86 (t, J = 7.5 Hz, 3 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 135.3, 132.8, 131.5, 129.2, 128.9, 126.2, 41.2, 38.8, 21.9, 21.0, 13.6, 13.1. Anal. Calcd for C₁₄H₁₉SBr: C, 56.19; H, 6.40. Found: C, 56.09; H, 6.27.
( E )- n -Pr(PhS)C=C(I) n -Pr: IR (neat): 2959, 1582, 1476, 1461 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.16-7.31 (m, 5 H), 2.94 (t, J = 7.3 Hz, 2 H), 2.39 (t, J = 7.3 Hz, 2 H), 1.50-1.66 (m, 4 H), 0.92 (t, J = 7.3 Hz, 3 H), 0.87 (t, J = 7.3 Hz, 3 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 135.5, 135.4, 129.3, 128.9, 126.4, 113.0, 45.4, 43.9, 22.9, 21.3, 13.5, 12.9. Anal. Calcd for C₁₄H₁₉SI: C, 48.56; H, 5.53. Found: C, 48.48; H, 5.47.

<A NAME="RU12007ST-8">8</A> Zask A. Helquist P. J. Org. Chem.  1978,  43:  1619 

<A NAME="RU12007ST-9">9</A>

( Z )- n -Pr(H)C=C(SPh) n -Pr: IR (neat): 2958, 1583, 1476 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.11-7.29 (m, 5 H), 5.90 (t, J = 7.1 Hz, 1 H), 2.31 (q, J = 7.2 Hz, 2 H), 2.14 (t, J = 7.2 Hz, 2 H), 1.36-1.56 (m, 4 H), 0.92 (t, J = 7.2 Hz, 3 H), 0.82 (t, J = 7.2 Hz, 3 H). The NOE was observed at two allyl positions {(CH₂CH=, 15%) and [=C(SPh)CH₂, 11%]} on irradiation at δ = 5.90 ppm (=CH). ¹³C NMR (67.5 MHz, CDCl₃): δ = 136.7, 135.8, 133.0, 129.2, 128.7, 125.6, 39.6, 31.9, 22.7, 21.6, 13.8, 13.3. Anal. Calcd for C₁₄H₂₀SBr: C, 76.30; H, 9.15. Found: C, 76.03; H, 8.92.

<A NAME="RU12007ST-10">10</A>

In the absence of bpy, the yield of 3 was 39% yield.

<A NAME="RU12007ST-11">11</A>

( E )- n -Pr(4-MeC ₆ H ₄ S)C=C(Br) n -Pr: IR (neat): 2960, 2929, 1894, 1602, 1491 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.15 (d, J = 8.3 Hz, 2 H), 7.09 (d, J = 8.3 Hz, 2 H), 2.90 (t, J = 7.4 Hz, 2 H), 2.34 (t, J = 7.4 Hz, 2 H), 2.32 (s, 3 H), 1.49-1.67 (m, 4 H), 0.93 (t, J = 7.4 Hz, 3 H), 0.86 (t, J = 7.4 Hz, 3 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 136.5, 132.2, 131.5, 131.4, 130.1, 129.8, 41.2, 38.5, 21.9, 21.0, 13.6, 13.1. Anal. Calcd for C₁₅H₂₁SBr: C, 57.50; H, 6.76. Found: C, 57.21; H, 6.67.
( E )- n -Pr(4-MeOC ₆ H ₄ S)C=C(Br) n -Pr: IR (neat): 2960, 2930, 1592, 1493 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.24 (d, J = 8.9 Hz, 2 H), 6.84 (d, J = 8.9 Hz, 2 H), 3.79 (s, 3 H), 2.91 (t, J = 7.3 Hz, 2 H), 2.28 (t, J = 7.5 Hz, 2 H), 1.48-1.68 (m, 4 H), 0.94 (t, J = 7.4 Hz, 3 H), 0.85 (t, J = 7.4 Hz, 3 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 159.2, 133.3, 132.8, 129.5, 125.1, 114.6, 55.3, 41.1, 38.0, 21.9, 20.9, 13.6, 13.1. Anal. Calcd for C₁₅H₂₁OSBr: C, 54.71; H, 6.43. Found: C, 54.53; H, 6.38.
( E )- n -Pr(4-BrC ₆ H ₄ S)C=C(Br) n -Pr: IR (neat): 2960, 2929, 1889, 1603, 1471 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.40 (d, J = 8.6 Hz, 2 H), 7.08 (d, J = 8.6 Hz, 2 H), 2.87 (t,
J = 7.2 Hz, 2 H), 2.37 (t, J = 7.7 Hz, 2 H), 1.49-1.67 (m, 4 H), 0.92 (t, J = 7.4 Hz, 3 H), 0.87 (t, J = 7.4 Hz, 3 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 134.7, 133.7, 132.0, 130.9, 130.2, 120.1, 41.3, 38.8, 21.9, 21.0, 13.6, 13.0. Anal. Calcd for C₁₄H₁₈SBr₂: C, 44.46; H, 4.80. Found: C, 44.32; H, 4.89.
( E )- n -Pr(MeS)C=C(Br) n -Pr: IR (neat): 2960, 2928, 1602, 1459 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 2.81 (t, J = 7.2 Hz, 2 H), 2.48 (t, J = 7.7 Hz, 2 H), 2.20 (s, 3 H), 1.54-1.63 (m, 4 H), 0.95 (t, J = 5.3 Hz, 3 H), 0.91 (t, J = 5.3 Hz, 3 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 133.4, 127.4, 40.8, 37.4, 21.7, 21.0, 16.4, 13.6, 12.9. Anal. Calcd for C₉H₁₇SBr: C, 45.57; H, 7.22. Found: C, 45.60; H, 6.93.
( E )- n -Pr( n -BuS)C=C(Br) n -Pr: IR (neat): 2960, 2929, 1601, 1462 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 2.84 (t,
J = 7.4 Hz, 2 H), 2.61 (t, J = 7.1 Hz, 2 H), 2.45 (t, J = 7.6 Hz, 2 H), 1.51-1.65 (m, 6 H), 1.36-1.48 (m, 2 H), 0.88-0.94 (m, 9 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 132.4, 128.9, 40.9, 37.8, 32.5, 31.9, 21.9, 21.8, 21.1, 13.6, 13.0. Anal. Calcd for C₁₂H₂₃SBr: C, 51.61; H, 8.30. Found: C, 51.36; H, 8.17.
( E )- n -Pr(BnS)C=C(Br) n -Pr: IR (neat): 2960, 2929, 1601, 1494, 1453 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.19-7.31 (m, 5 H), 3.80 (s, 2 H), 2.65 (t, J = 7.2 Hz, 2 H), 2.48 (t, J = 7.5 Hz, 2 H), 1.53-1.67 (m, 2 H), 1.36-1.49 (m, 2 H), 0.94 (t, J = 7.4 Hz, 3 H), 0.81 (t, J = 7.4 Hz, 3 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 137.8, 131.8, 131.5, 128.8, 128.5, 127.0, 40.7, 38.5, 37.9, 21.7, 21.0, 13.6, 12.9. Anal. Calcd for C₁₅H₂₁SBr: C, 57.50; H, 6.76. Found: C, 57.15; H, 6.85.
( E )- n -Pr(PhSe)C=C(Br) n -Pr: IR (neat): 2959, 2929, 1608, 1577, 1475 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.36-7.42 (m, 2 H), 7.23-7.28 (m, 3 H), 2.89 (t, J = 7.4 Hz, 2 H), 2.41 (t, J = 7.4 Hz, 2 H), 1.46-1.69 (m, 4 H), 0.92 (t, J = 7.2 Hz, 3 H), 0.86 (t, J = 7.2 Hz, 3 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 132.1, 130.6, 129.5, 129.3, 129.2, 127.1, 43.3, 40.7, 21.9, 21.3, 13.5, 13.0. Anal. Calcd for C₁₄H₁₉SeBr: C, 48.58; H, 5.53. Found: C, 48.82; H, 5.54.
( E )-Ph(Br)C=C(SPh)Me: IR (neat): 3057, 1581, 1475, 1439 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.24-7.41 (m, 10 H), 2.21 (s, 3 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 140.5, 134.5, 130.5, 130.2, 129.1, 129.0, 128.5, 128.1, 126.9, 123.3, 24.9. Anal. Calcd for C₁₅H₁₃SBr: C, 59.02; H, 4.29. Found: C, 58.94; H, 4.37.
( E )-Ph(Br)C=C(SPh)CH ₂ OAc: IR (neat): 3058, 1743, 1581, 1477, 1440 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.20-7.41 (m, 10 H), 4.96 (s, 2 H), 2.00 (s, 3 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 170.4, 139.7, 133.9, 130.3, 129.4, 129.3, 129.0, 128.8, 128.1, 127.2, 66.2, 20.6. Anal. Calcd for C₁₇H₁₅O₂SBr: C, 56.21; H, 4.16. Found: C, 56.32; H, 4.25.

<A NAME="RU12007ST-12">12</A>

The stereochemistry of compounds in entries 12 and 14 was determined by NOE after the debromination.

<A NAME="RU12007ST-13">13</A> For the preparation of PhSCu, see: Adams R. Reifschneider W. Ferretti A. Org. Synth., Coll. Vol. V   John Wiley & Sons; New York: 1973.  p.107-110  

<A NAME="RU12007ST-14">14</A> Takeuchi H. Hiyama T. Kamai N. Oya H. J. Chem. Soc., Perkin Trans. 2  1997,  2301 

<A NAME="RU12007ST-15">15</A>

When PhSCu was treated with acetic acid, (PhS)₂ was obtained in 80% yield.