RSS-Feed abonnieren
DOI: 10.1055/s-2006-948174
Synthesis of (E)-1-Aryl Alk-1-en-3-ones by Tetraphosphine/Palladium-Catalysed Heck Reactions of Alk-1-en-3-ones with Aryl Bromides
Publikationsverlauf
Publikationsdatum:
04. August 2006 (online)
![](https://www.thieme-connect.de/media/synlett/200618/lookinside/thumbnails/10.1055-s-2006-948174-1.jpg)
Abstract
The tetraphosphine cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane in combination with [Pd(C3H5)Cl]2 affords a very efficient catalyst for the Heck reaction of alk-1-en-3-ones with aryl bromides. If appropriate reaction conditions are used (NaOAc as base, hydroquinone as stabilising agent and DMF as solvent) high yields of (E)-1-aryl alk-1-en-3-one derivatives are obtained. In general, higher reaction rates were observed with electron-poor aryl bromides, but the electron-rich aryl bromides 4-N,N-dimethylaminobromobenzene and 4-bromoanisole also led to the arylated enones. Even with sterically very congested aryl bromides such as 9-bromoanthracene, 2,4,6-trimethylbromobenzene or 2,4,6-triisopropylbromobenzene, the expected (E)-1-aryl alk-1-en-3-ones were obtained in moderate to good yields. Moreover, several reactions can be performed with as little as 0.1% catalyst.
Key words
Tedicyp - Heck reaction - (E)-1-aryl alk-1-en-3-one derivatives
- 1
Beletskaya I.Cheprakov A. Chem. Rev. 2000, 100: 3009 - 2
Withcombe N.Hii (Mimi) KK.Gibson S. Tetrahedron 2001, 57: 7449 - 3
Littke A.Fu G. Angew. Chem. Int. Ed. 2002, 41: 4176 - 4
Farina V. Adv. Synth. Catal. 2004, 346: 1553 - For Heck vinylations with alk-1-en-3-ones and aryl iodides, see:
-
5a
Ziegler FE.Chakraborty UR.Weisenfeld RB. Tetrahedron 1981, 37: 4035 -
5b
Cacchi S.Arcadi A. J. Org. Chem. 1983, 48: 4236 -
5c
Jeffery T. J. Chem. Soc., Chem. Commun. 1984, 1287 -
5d
Cacchi S.Palmieri G. Synthesis 1984, 575 -
5e
Ohff M.Ohff A.van der Boom ME.Milstein D. J. Am. Chem. Soc. 1997, 119: 11687 -
5f
Anson MS.Mirza AR.Tonks L.Williams JMJ. Tetrahedron Lett. 1999, 40: 7147 -
5g
Cacchi S.Fabrizi G.Gasparrini F.Villani C. Synlett 1999, 345 -
5h
Hagiwara H.Shimizu Y.Hoshi T.Suzuki T.Ando M.Ohkubo K.Yokoyama C. Tetrahedron Lett. 2001, 42: 4349 -
5i
Cacchi S.Fabrizi G.Goggiamani A. Arkivoc 2003, (viii): 58 -
5j
Bianco A.Cavarischia C.Farina A.Guiso M.Marra C. Tetrahedron Lett. 2003, 44: 9107 -
5k
Botella L.Najera C. Tetrahedron Lett. 2004, 45: 1833 -
5l
Cesati RR.de Armas J.Hoveyda AH. J. Am. Chem. Soc. 2004, 126: 96 -
5m
Yang D.Chen Y.-C.Zhu N.-Y. Org. Lett. 2004, 6: 1577 -
5n
Gupta AK.Song CH.Oh CH. Tetrahedron Lett. 2004, 45: 4113 -
5o
Bianco A.Cavarischia C.Guiso M. Eur. J. Org. Chem. 2004, 2894 - 6
Aslam M.Elango V.Davenport KG. Synthesis 1989, 869 - 7
Semmelhack MF.Ho S.Cohen D.Streigerwald M.Lee MC.Lee G.Gilbert AM.Wulff WD.Ball RG. J. Am. Chem. Soc. 1994, 116: 7108 - 8
Hagiwara H.Eda Y.Morohashi K.Suzuki T.Ando M.Ito N. Tetrahedron Lett. 1998, 39: 4055 - 9
Uchiro H.Nagasawa K.Aiba Y.Kobayashi S. Tetrahedron Lett. 2000, 41: 4165 - 10
Uchiro H.Nagasawa K.Sawa T.Hasegawa D.Kotake T.Sugiura Y.Kobayashi S.Otoguro K.Omura S. Bioorg. Med. Chem. Lett. 2002, 12: 2699 - 11
Xu X.Fakha G.Sinou D. Tetrahedron 2002, 58: 7539 - 12
Nakamura M.Mamino M.Masaki M.Maki S.Matsui R.Kojima S.Hirano T.Ohmiya Y.Niwa H. Tetrahedron Lett. 2005, 46: 53 - 13
Laurenti D.Feuerstein M.Pèpe G.Doucet H.Santelli M. J. Org. Chem. 2001, 66: 1633 - 14
Feuerstein M.Laurenti D.Bougeant C.Doucet H.Santelli M. Chem. Commun. 2001, 325 - 15
Feuerstein M.Berthiol F.Doucet H.Santelli M. Org. Biomol. Chem. 2003, 1: 2235 -
16a
Feuerstein M.Doucet H.Santelli M. J. Org. Chem. 2001, 66: 5923 -
16b
Feuerstein M.Doucet H.Santelli M. Tetrahedron Lett. 2002, 43: 2191 -
16c
Berthiol F.Doucet H.Santelli M. Tetrahedron Lett. 2003, 44: 1221 -
16d
Berthiol F.Doucet H.Santelli M. Tetrahedron Lett. 2004, 45: 5633 -
16e
Berthiol F.Doucet H.Santelli M. Eur. J. Org. Chem. 2005, 1367 -
16f
Berthiol F.Doucet H.Santelli M. Synthesis 2005, 3589 -
16g
Lemhadri M.Doucet H.Santelli M. Tetrahedron 2004, 50: 11533 -
16h
Kondolff I.Doucet H.Santelli M. Eur. J. Org. Chem. 2006, 765
References and Notes
DMF 99.8%, sodium acetate 99%, aryl halides and alk-1-en-3-ones were not purified before use. All reactions were run under argon in Schlenk tubes. As a typical experiment, the reaction of aryl halide (1 mmol), alk-1-en-3-one (2 or 4 mmol, see Table [1] and Table [2] ), hydroquinone (9 mg, 0.08 mmol) and NaOAc (164 mg, 2 mmol) at 110 °C during 20 h in dry DMF (3 mL) with cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane-0.5[PdCl(C3H5)]2 complex under argon affords the corresponding (E)-1-aryl alk-1-en-3-one after addition of H2O (20 mL), extraction with CH2Cl2 (20 mL), separation, drying (MgSO4), evaporation and purification by chromatography on silica gel.
18All new compounds gave satisfactory 1H NMR, 13C NMR and elemental analyses. 1H (300 MHz), 13C NMR (75 MHz) in CDCl3 and elemental analyses of selected products: compound 9: 1H NMR: δ = 9.09 (s, 1 H), 8.26 (s, 1 H), 8.11 (d, J = 8.5 Hz, 1 H), 7.85 (d, J = 8.5 Hz, 1 H), 7.75 (t, J = 7.8 Hz, 1 H), 7.66 (d, J = 16.1 Hz, 1 H), 7.58 (t, J = 7.8 Hz, 1 H), 6.94 (d, J = 16.1 Hz, 1 H), 2.44 (s, 3 H). 13C NMR: δ = 197.7, 149.3, 139.7, 135.7, 130.8, 129.5, 128.4, 128.3, 127.6, 127.5, 127.4, 127.0, 27.9. Anal. Calcd for C13H11NO (197): C, 79.16; H, 5.62. Found: C, 79.42; H, 5.69.
Compound 20: 1H NMR: δ = 7.78 (d, J = 16.4 Hz, 1 H), 7.02 (s, 2 H), 6.23 (d, J = 16.4 Hz, 1 H), 3.08 (sept, J = 6.8 Hz, 2 H), 2.88 (sept, J = 6.8 Hz, 1 H), 2.70 (q, J = 7.4 Hz, 2 H), 1.28-1.12 (m, 21 H). 13C NMR: δ = 200.6, 148.9, 146.3, 142.0, 132.6, 130.4, 120.8, 34.3, 34.1, 30.2, 24.0, 23.9, 8.1. Anal. Calcd for C20H30O (286): C, 83.86; H, 10.56. Found: C, 84.02; H, 10.78.
Compound 25: 1H NMR: δ = 8.19 (d, J = 8.3 Hz, 2 H), 7.67 (d, J = 8.3 Hz, 2 H), 7.53 (d, J = 16.5 Hz, 1 H), 6.80 (d, J = 16.5 Hz, 1 H), 2.64 (t, J = 7.4 Hz, 2 H), 1.69 (sext, J = 7.4 Hz, 2 H), 0.94 (t, J = 7.4 Hz, 3 H). 13C NMR: δ = 199.7, 148.5, 140.8, 139.0, 129.5, 128.7, 124.1, 43.3, 17.5, 13.7. Anal. Calcd for C12H13NO3 (219): C, 65.74; H, 5.98. Found: C, 65.61; H, 6.12.
Compound 27: 1H NMR: δ = 7.49 (d, J = 16.0 Hz, 1 H), 7.43 (d, J = 8.4 Hz, 2 H), 6.67 (d, J = 8.4 Hz, 2 H), 6.55 (d, J = 16.0 Hz, 1 H), 3.01 (s, 6 H), 2.60 (t, J = 7.4 Hz, 2 H), 1.69 (sext, J = 7.4 Hz, 2 H), 0.96 (t, J = 7.4 Hz, 3 H). 13C NMR: δ = 200.7, 151.8, 143.2, 130.0, 122.2, 121.6, 111.8, 42.4, 40.1, 18.2, 13.9. Anal. Calcd for C14H19NO (217): C, 77.38; H, 8.81. Found: C, 77.19; H, 8.80.