Subscribe to RSS
DOI: 10.1055/s-2007-984502
Gold-Catalyzed Cyclizations of 1,7-Enynes
Publication History
Publication Date:
25 June 2007 (online)
Abstract
The skeletal rearrangement as well as the hydroxy- and methoxycyclization of 1,7-enynes proceeds at room temperature with cationic gold(I) catalysts.
Key words
gold - enynes - alkynes - cycloisomerization - rearrangements
- 1
Jiménez-Núñez E.Echavarren AM. Chem. Commun. 2007, 333 - 2
Zhang L.Sunm J.Kozmin SA. Adv. Synth. Catal. 2006, 348: 2271 -
3a
Hashmi ASK.Hutchings GJ. Angew. Chem. Int. Ed. 2006, 45: 7896 -
3b
Ma S.Yu S.Gu Z. Angew. Chem. Int. Ed. 2005, 44: 200 -
4a
Lloyd-Jones GC. Org. Biomol. Chem. 2003, 1: 215 -
4b
Aubert C.Buisine O.Malacria M. Chem. Rev. 2002, 102: 813 -
4c
Diver ST.Giessert AJ. Chem. Rev. 2004, 104: 1317 -
4d
Echavarren AM.Nevado C. Chem. Soc. Rev. 2004, 33: 431 - 5
Nieto-Oberhuber C.López S.Jiménez-Núñez E.Echavarren AM. Chem. Eur. J. 2006, 11: 5916 - 6
Nieto-Oberhuber C.López S.Muñoz MP.Cárdenas DJ.Buñuel E.Nevado C.Echavarren AM. Angew. Chem. Int. Ed. 2005, 44: 6146 -
7a
Nieto-Oberhuber C.Muñoz MP.Buñuel E.Nevado C.Cárdenas DJ.Echavarren AM. Angew. Chem. Int. Ed. 2004, 43: 2402 -
7b
Nieto-Oberhuber C.Muñoz MP.López S.Jiménez-Núñez E.Nevado C.Herrero-Gómez E.Raducan M.Echavarren AM. Chem. Eur. J. 2006, 11: 1677 -
8a
Méndez M.Muñoz MP.Echavarren AM. J. Am. Chem. Soc. 2000, 122: 11549 -
8b
Méndez M.Muñoz MP.Nevado C.Cárdenas DJ.Echavarren AM. J. Am. Chem. Soc. 2001, 123: 10511 - 9
Nevado C.Cárdenas DJ.Echavarren AM. Chem. Eur. J. 2003, 9: 2627 - 10
Shibata T.Kobayashi Y.Maekawa S.Toshida N.Takagi K. Tetrahedron 2005, 61: 9018 -
11a
Toullec PY.Genin E.Leseurre L.Genêt J.-P.Michelet V. Angew. Chem. Int. Ed. 2006, 45: 7427 -
11b
Amijs CHM.Ferrer C.Echavarren AM. Chem. Commun. 2007, 698 - 12
Ferrer C.Raducan M.Nevado C.Claverie CK.Echavarren AM. Tetrahedron 2007, 63: 6306 - 13
Zhang L.Kozmin SA. J. Am. Chem. Soc. 2005, 127: 6962 - 14
Chatai N.Morimoto T.Muto T.Murai S. J. Am. Chem. Soc. 1994, 116: 6049 -
15a
Chatani N.Furukawa N.Sakurai H.Murai S. Organometallics 1996, 15: 901 -
15b
Miyanohana Y.Inoue H.Chatani N. J. Org. Chem. 2004, 69: 8541 - 16
Oh CH.Bang SY.Rgim CY. Bull. Korean Chem. Soc. 2003, 24: 887 - 17
Chatani N.Inoue H.Morimoto T.Muto T.Murai S. J. Org. Chem. 2001, 66: 4433 -
18a
Chatani N.Inoue H.Kotsuma T.Murai S. J. Am. Chem. Soc. 2002, 124: 10294 -
18b
Kim SM.Lee SI.Cheng YK. Org. Lett. 2006, 8: 5425 -
18c
Simmons EM.Sarpong R. Org. Lett. 2006, 8: 2883 - 19
Miyanohana Y.Chatani N. Org. Lett. 2006, 8: 2155 - 20 A single result has been reported by using [Pt(dppp)(PhCN)2](BF4)2 at r.t., although the yield was only 27% after 20 h:
Oi S.Tsukamoto I.Miyano S.Inoue Y. Organometallics 2001, 20: 3704 - 21
Ochida A.Ito H.Sawamura M. J. Am. Chem. Soc. 2006, 128: 16486 - 22
Nishizawa M.Yadav VK.Skwarczynski M.Takao H.Imagawa H.Sugihara T. Org. Lett. 2003, 5: 1609 - 23
Compadre CM.Pezzuto JM.Kinghorn AD.Kamath SK. Science 1985, 227: 417 - Synthesis of hernandulcin:
-
24a
Kim JH.Lim HJ.Cheon SH. Tetrahedron Lett. 2002, 43: 4721 -
24b
Mori K.Kato M. Tetrahedron 1986, 42: 5895 -
24c
Mori K.Kato M. Tetrahedron Lett. 1986, 27: 981 -
25a
Nieto-Oberhuber C.López S.Echavarren AM. J. Am. Chem. Soc. 2005, 127: 6178 -
25b
Herrero-Gómez E.Nieto-Oberhuber C.López S.Benet-Buchholz J.Echavarren AM. Angew. Chem. Int. Ed. 2006, 45: 5455 - 26
Nieto-Oberhuber C.López S.Muñoz MP.Jiménez-Núñez E.Buñuel E.Cárdenas DJ.Echavarren AM. Chem. Eur. J. 2006, 11: 1694 - 27
López S.Herrero-Gómez E.Pérez-Galán P.Nieto-Oberhuber C.Echavarren AM. Angew. Chem. Int. Ed. 2006, 45: 6029 -
28a
Trost BM.Trost MK. Tetrahedron Lett. 1991, 32: 3647 -
28b
Fürstner A.Stelzer F.Szillat H. J. Am. Chem. Soc. 2001, 123: 11863 -
32a
Strieter ER.Blackmond DG.Buchwald SL. J. Am. Chem. Soc. 2003, 125: 13978 -
32b
Walker SD.Border TE.Martinelli JR.Buchwald SL. Angew. Chem. Int. Ed. 2004, 43: 1871 -
32c
Kaye S.Fox JM.Hicks FA.Buchwald SL. Adv. Synth. Catal. 2001, 343: 789 - 34
Kocienski P.Wadman S.Cooper K. J. Org. Chem. 1989, 54: 1215 - 35
Tanigawa Y.Kanamaru H.Sonoda A.Murahashi S.-I. J. Am. Chem. Soc. 1977, 99: 2361
References and Notes
General Procedure for Au(I)-Catalyzed Skeletal Rearrangement of Enynes
To a mixture of the cationic Au(I) complex (2 mol%) in dry CH2Cl2 (1 mL) was added the enyne in dry CH2Cl2 (1 mL) and the mixture was stirred for the time and at the temperature stated in Table
[1]
. The resulting mixture was filtered through SiO2 and the solvent was evaporated to give the corresponding product.
Selected Characterization Data
Compound 18b (9:1 E/Z): yellow oil. 1H NMR (400 MHz, CDCl3): δ = 6.04 (d, J = 15.7 Hz, 1 H), 5.64 (tt, J = 7.5, 1.4 Hz, 1 H), 5.55 (br s, 1 H), 2.67 (s, 2 H), 3.74 (s, 6 H), 2.18 (br s, 2 H), 2.13 (q, J = 5.6 Hz, 2 H), 1.75 (d, J = 6.6 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 172.2, 133.6, 133.1, 124.7, 122.6, 53.5, 52.8, 30.3, 27.8, 22.9, 18.4. ESI-HRMS: m/z calcd for C13H18NaO4 [M + Na]+: 261.1103; found: 261.1111.
Compound 18c: colorless oil. 1H NMR (400 MHz, CDCl3): δ = 7.40 (d, J = 7.6 Hz, 2 H), 7.31 (t, J = 7.6 Hz, 2 H), 7.20 (t, J = 7.6 Hz, 1 H), 6.78 (d, J = 16.3 Hz, 1 H), 6.52 (d, J = 16.3 Hz, 1 H), 5.84 (s, 1 H), 3.76 (s, 6 H), 2.85 (s, 2 H), 2.29 (s, 2 H), 2.19 (t, J = 6.3 Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ = 172.1, 137.7, 133.2, 131.2, 128.7, 128.6, 127.3, 126.4, 125.9, 53.5, 52.9, 30.3, 27.7, 23.3. ESI-HRMS: m/z calcd for C18H20NaO4 [M + Na]+: 323.1259; found: 323.1269.
Compound 18e: colorless oil. 1H NMR (400 MHz, CDCl3): δ = 8.03 (dd, J = 8.2, 1.4 Hz, 4 H), 7.69 (dq, J = 14.4, 6.6 Hz, 1 H), 7.56 (tt, J = 8.2, 1.7 Hz, 1 H), 5.98 (d, J = 15.7 Hz, 1 H), 5.57 (s, 1 H), 5.46 (dq, J = 6.6, 15.7 Hz, 1 H), 2.94 (s, 2 H), 2.44-2.42 (m, 4 H), 1.74 (dd, J = 0.7, 6.6 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 136.9, 134.7, 132.8, 131.4, 130.3, 128.8, 124.9, 122.9, 87.9, 25.7, 23.8, 22.8, 18.4. ESI-HRMS: m/z calcd for C21H22NaO4S2 [M + Na]+: 425.0857; found: 425.0853.
Compound 18f: colorless oil. 1H NMR (400 MHz, CDCl3): δ = 8.06 (dd, J = 8.4, 1.3 Hz, 1 H), 7.69 (tt, J = 7.5, 1.1 Hz, 1 H), 7.56 (t, J = 8.2 Hz, 4 H), 7.38-7.31 (m, 4 H), 7.26-7.22 (m, 1 H), 6.71 (d, J = 16.4 Hz, 1 H), 6.32 (d, J = 16.3 Hz, 1 H), 5.80 (br s, 1 H), 3.12 (s, 2 H), 2.53 (br s, 2 H), 2.49 (d, J = 5.6 Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ = 137.3, 136.8, 134.8, 131.4, 130.4, 130.3, 128.9, 128.7, 127.7, 126.5, 126.2, 87.7, 25.5, 23.9, 23.4. ESI-HRMS: m/z calcd for C26H24NaO4S2 [M + Na]+: 487.1014; found: 487.1004.
Compound 18g: colorless oil. 1H NMR (400 MHz, CDCl3): δ = 8.03 (d, J = 7.8 Hz, 4 H), 7.69 (t, J = 7.4 Hz, 2 H), 7.56 (t, J = 7.8 Hz, 4 H), 5.45 (s, 1 H), 5.35 (s, 1 H), 2.80 (s, 2 H), 2.41 (s, 4 H), 1.73 (s, 3 H), 1.69 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 137.0, 135.4, 134.6, 131.4, 128.8, 125.3, 123.8, 88.1, 29.7, 26.7, 23.3, 22.7, 19.9. ESI-HRMS: m/z calcd for C22H24NaO4S2 [M + Na]+: 439.1014; found: 439.1013.
Compound 18h: light yellow oil. 1H NMR (400 MHz, CDCl3): δ = 8.03 (d, J = 7.8 Hz, 4H), 7.69 (t, J = 7.4 Hz, 2 H), 7.56 (t, J = 7.8 Hz, 4 H), 5.45 (s, 1 H), 5.35 (s, 1 H), 2.80 (s, 2 H), 2.41 (s, 4 H), 1.73 (s, 3 H), 1.69 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 143.6, 136.1, 133.6, 131.9, 129.8, 127.9, 123.3, 122.4, 47.8, 42.7, 26.8, 25.5, 21.7, 19.8. ESI-HRMS: m/z calcd for C16H21NNaO2S [M + Na]+: 314.1191; found: 314.1185.
General Procedure for Au(I)-Catalyzed Intramolecular Hydroxycyclization or Alkoxycyclization
The enyne was added to a mixture of the Au(I) catalyst (5-10 mol%) and silver(I) salt (5-10 mol%) [or the corresponding cationic Au(I) complex] in the stated solvent [3 mL of MeOH or 3 mL of aq acetone (2 equiv H2O)] and the mixtures were stirred under the stated conditions. The resulting mixture was filtered through SiO2, and the solvent was evaporated. Flash column chromatography (3:1 hexane-EtOAc) gave the corresponding product.
Compound 22b: 1H NMR (400 MHz, CDCl3): δ = 8.07 (dd, J = 1.2, 7.4 Hz, 2 H), 7.98 (dd, J = 1.2, 7.4 Hz, 2 H), 7.70-7.66 (m, 2 H), 7.56 (t, J = 7.7 Hz, 4 H), 5.03 (s, 1 H), 4.92 (s, 1 H), 3.24 (d, J = 15.1 Hz, 1 H), 2.92 (s, 3 H), 2.88 (d, J = 15.1 Hz, 1 H), 2.63-2.58 (m, 1 H), 2.26 (m, 2 H), 2.02-1.97 (m, 2 H), 1.12 (s, 3 H), 1.05 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 140.3, 137.4, 136.9, 134.52, 134.48, 131.64, 131.63, 128.8, 128.6, 117.5, 89.2, 77.4, 48.9, 48.5, 34.2, 24.9, 23.4, 22.8, 21.9. ESI-HRMS: m/z calcd for C23H28NaO5S2 [M + Na]+: 471.1276; found: 471.1270.
Compound 23: 1H NMR (400 MHz, CDCl3): δ = 8.09 (d, J = 7.6 Hz, 2 H), 8.05 (d, J = 7.6 Hz, 2 H), 7.75-7.70 (m, 2 H), 7.64 (t, J = 7.9 Hz, 2 H), 7.59 (t, J = 7.9 Hz, 2 H), 7.35-7.29 (m, 5 H), 4.97 (d, J = 5.7 Hz, 1 H), 4.90 (s, 1 H), 4.88 (s, 1 H), 3.15 (d, J = 15.6 Hz, 1 H), 2.92 (d, J = 15.6 Hz, 1 H), 2.65-2.56 (m, 2 H), 2.36-2.26 (m, 2 H), 2.25-2.16 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ = 142.8, 140.9, 136.6, 136.5, 134.8, 131.7, 131.6, 128.8, 128.7, 127.8, 126.3, 114.5, 88.5, 74.3, 53.6, 47.5, 33.7, 31.1, 24.4. ESI-HRMS: m/z calcd for C26H26NaO5S2 [M + Na]+: 505.1119; found: 505.1115.
Compound 31a: 1H NMR (400 MHz, CDCl3): δ = 8.07 (dd, J = 1.1, 8.5 Hz, 2 H), 8.02 (dd, J = 1.1, 8.5 Hz, 2 H), 7.72-7.68 (m, 2 H), 7.60-7.55 (m, 4 H), 5.08 (overlap. t, J = 7.1 Hz, 1 H), 5.06 (overlap. s, 1 H), 4.94 (s, 1 H), 3.29 (d, J = 15.4 Hz, 1 H), 2.89 (d, J = 15.4 Hz, 1 H), 2.59-2.54 (m, 1 H), 2.34-2.26 (m, 2 H), 2.04-1.98 (m, 4 H), 1.69 (s, 3 H), 1.61 (s, 3 H), 1.51-1.43 (m, 1 H), 1.49-1.36 (m, 2 H), 1.13 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 140.2, 137.1, 136.7, 134.6, 134.6, 132.3, 131.8, 131.7, 128.8, 128.7, 124.2, 118.3, 88.7, 75.1, 48.5, 39.7, 34.1, 25.9, 25.3, 25.2, 23.0, 21.4, 17.9. ESI-HRMS: m/z calcd for C27H34NaO5S2 [M + Na]+: 525.1745; found: 525.1767.
Compound 31b: colorless oil. 1H NMR (400 MHz, CDCl3): δ = 8.10 (d, J = 7.3 Hz, 2 H), 8.01 (d, J = 7.3 Hz, 2 H), 7.72-7.68 (m, 2 H), 7.59 (td, J = 7.7, 2.5 Hz, 4 H), 5.07 (m, 2 H), 4.92 (s, 1 H) 3.25 (d, J = 15.1 Hz, 1 H), 2.96 (s, 3 H), 2.89 (d, J = 15.1 Hz, 1 H), 2.65-2.58 (m, 1 H), 2.44 (t, J = 6.5 Hz, 1 H), 2.34-2.27 (m, 1 H), 2.02-1.86 (m, 4 H), 1.69 (s, 3 H), 1.61 (s, 3 H), 1.54-1.49 (m, 2 H), 1.06 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 140.4, 137.4, 136.9, 134.6, 134.5, 131.8, 131.7, 128.8, 128.6, 124.4, 117.5, 89.2, 79.2, 48.5, 45.4, 35.2, 34.4, 25.9, 25.1, 22.9, 21.5, 20.6, 17.9. ESI-HRMS: m/z calcd for C28H36NaO5S2 [M + Na]+: 539.1902; found: 539.1884.
Compound 10a: colorless oil. 1H NMR (400 MHz, CDCl3): δ = 8.06 (d, J = 7.6 Hz, 2 H), 8.03 (d, J = 7.4 Hz, 2 H), 7.71 (t, J = 7.2 Hz, 2 H), 7.59 (t, J = 7.9 Hz, 4 H), 5.08 (m, 1 H), 5.01 (s, 1 H), 3.24 (d, J = 15.4 Hz, 1 H), 2.92 (d, J = 15.4 Hz, 1 H), 2.55 (dt, J = 15.5, 4.6 Hz, 1 H), 2.37 (t, J = 7.9 Hz, 1 H), 2.32-2.25 (m, 1 H), 2.07-1.93 (m, 4 H), 1.69 (s, 3 H), 1.62 (s, 3 H), 1.53 (br s, 1 H), 1.46 (t, J = 8.2 Hz, 2 H), 1.12 (s, 3 H). 13C NMR (CDCl3): δ = 139.9, 137.0, 136.6, 134.7, 132.1, 131.8, 131.7, 128.8, 128.7, 124.4, 118.6, 88.5, 74.6, 48.2, 40.1, 34.2, 25.9, 25.3, 24.2, 22.5, 21.8, 17.9. ESI-HRMS: m/z calcd for C27H34NaO5S2 [M + Na]+: 525.1745; found: 525.1743.
Compound 10b: colorless oil. 1H NMR (400 MHz, CDCl3): δ = 8.07 (d, J = 7.4 Hz, 2 H), 8.03 (d, J = 7.3 Hz, 2 H), 7.70 (t, J = 7.9 Hz, 2 H), 7.59 (td, J = 8.2, 1.8 Hz, 4 H), 5.05 (m, 3 H), 3.22 (d, J = 15.3 Hz, 1 H), 3.02 (s, 3 H), 2.91 (d, J = 15.3 Hz, 1 H), 2.61-2.55 (m, 1 H), 2.46 (t, J = 7.7 Hz, 1 H), 2.33-2.26 (m, 1 H), 1.99-1.85 (m, 4 H), 1.70 (s, 3 H), 1.61 (s, 3 H), 1.45 (t, J = 8.6 Hz, 2 H), 1.11 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 139.6, 137.2, 136.9, 134.6, 131.7, 128.8, 128.7, 124.5, 117.7, 88.9, 79.3, 48.7, 45.3, 35.0, 34.9, 25.9, 25.4, 22.5, 22.0, 19.7, 17.9. ESI-HRMS: m/z calcd for C28H36NaO5S2 [M + Na]+: 539.1902; found: 539.1890.
Compound 32: colorless oil. 1H NMR (400 MHz, CDCl3): δ = 8.05 (d, J = 7.5 Hz, 4 H), 7.70 (t, J = 7.6 Hz, 2 H), 7.58 (t, J = 7.9 Hz, 4 H), 5.50 (s, 1 H), 5.37 (s, 1 H), 5.10 (t, J = 6.2 Hz, 1 H), 2.84 (s, 2 H), 2.42 (s, 4 H), 2.12-2.01 (m, 4 H), 1.70 (s, 6 H), 1.63 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 138.8, 137.0, 134.7, 131.9, 131.4, 129.9, 128.8, 125.1, 124.1, 123.9, 88.1, 40.6, 29.7, 26.9, 25.9, 23.3, 22.8, 18.3, 17.9. ESI-HRMS: m/z calcd for C27H32NaO4S2 [M + Na]+: 507.1640; found: 507.1646.
Compound 33: colorless oil. 1H NMR (400 MHz, CDCl3): δ = 8.04 (d, J = 8.5 Hz, 4 H), 7.70 (t, J = 6.8 Hz, 2 H), 7.57 (t, J = 8.0 Hz, 4 H), 5.49 (s, 1 H), 5.38 (s, 1 H) 5.07 (t, J = 6.4 Hz, 1 H), 2.79 (s, 2 H), 2.40 (s, 4 H), 2.10-2.03 (m, 4 H), 1.73 (s, 3 H), 1.68 (s, 3 H), 1.59 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 139.2, 136.9, 134.7, 134.6, 132.0, 131.8, 131.4, 129.8, 128.8, 128.7, 125.9, 124.1, 123.2, 88.0, 48.6, 33.2, 29.7, 27.2, 25.9, 23.9, 23.3, 22.7, 17.8. ESI-HRMS: m/z calcd for C27H32NaO4S2 [M + Na]+: 507.1640; found: 507.1637.