RSS-Feed abonnieren
DOI: 10.1055/s-2003-37532
Iridium Complex-Catalyzed Pauson-Khand-Type Reaction of Allenynes
Publikationsverlauf
Publikationsdatum:
26. Februar 2003 (online)
![](https://www.thieme-connect.de/media/synlett/200304/lookinside/thumbnails/10.1055-s-2003-37532-1.jpg)
Abstract
Vaska’s complex [IrCl(CO)(PPh3)2] efficiently catalyzes the intramolecular carbonylative [2+2+1] cycloaddition of allenynes. A dimethyl substituent on the allene terminus and a low partial pressure of carbon monoxide realize the selective engagement of the internal π-bond of allene.
Key words
alkynes - allenes - carbonylations - iridium - Pauson-Khand reaction
-
1a
Lautens M.Klute W.Tam W. Chem. Rev. 1996, 96: 49 -
1b
Ojima I.Tzamarioudaki M.Li Z.Donoban RJ. Chem. Rev. 1996, 96: 635 -
1c
Frühauf H.-W. Chem. Rev. 1997, 97: 523 - Recent reviews of the Pauson-Khand(-type) reaction:
-
2a
Jeong N. In Transition Metals In Organic Synthesis Vol. 1:Beller M.Bolm C. Wiley-VCH; Weinheim: 1998. p.560 -
2b
Chung YK. Coord. Chem. Rev. 1999, 188: 297 -
2c
Hanson BE. Comments on Inorg. Chem. 2002, 23: 289 - Recent examples of Co catalysts:
-
3a
Jeong N.Hwang SH. Angew. Chem. Int. Ed. 2000, 39: 636 -
3b
Kim S.-W.Son SU.Lee SI.Hyeon T.Chung YK. J. Am. Chem. Soc. 2000, 122: 1550 -
3c
Comely AC.Gibson SF.Stevenazzi A.Hales NJ. Tetrahedron Lett. 2001, 42: 1183 -
3d
Sugihara T.Yamaguchi M.Nishizawa M. Chem.-Eur. J. 2001, 7: 1589 -
3e
Krafft ME.Boñaga LVR.Hirosawa J. J. Org. Chem. 2001, 66: 3004 - Recent examples of Rh catalysts:
-
4a
Kobayashi T.Koga Y.Narasaka K. J. Orgmet. Chem. 2001, 624: 73 -
4b
Jeong N.Sung BK.Choi YK. J. Am. Chem. Soc. 2000, 122: 6771 -
4c
Evans PA.Robinson JE. J. Am. Chem. Soc. 2001, 123: 4609 -
4d
Morimoto T.Fuji K.Tsutsumi K.Kakiuchi K. J. Am. Chem. Soc. 2002, 124: 3806 -
4e
Shibata T.Toshida N.Takagi K. Org. Lett. 2002, 4: 1619 - 5
Aumann R.Weidenhaupt H.-J. Chem. Ber. 1987, 120: 23 -
6a
Ahmar M.Antras F.Cazes B. Tetrahedron Lett. 1995, 36: 4417 -
6b
Antras F.Ahmar M.Cazes B. Tetrahedron Lett. 2001, 42: 8153 -
7a
Narasaka K.Shibata T. Chem. Lett. 1994, 315 -
7b
Shibata T.Koga K.Narasaka K. Bull. Chem. Soc. Jpn. 1995, 68: 911 - 8
Ahmar M.Locatelli C.Colombier D.Cazes B. Tetrahedron Lett. 1997, 38: 5281 -
9a
Mukai C.Nomura I.Yamanishi K.Hanaoka M. Org. Lett. 2002, 4: 1755 -
9b
Brummond KM.Chen H.Fisher KD.Kerekes AD.Rickards B.Sill PC.Geib SJ. Org. Lett. 2002, 4: 1931 -
10a
Kent JL.Wan H.Brummond KM. Tetrahedron Lett. 1995, 36: 2407 -
10b
Brummond KM.Wan H.Kent JL. J. Org. Chem. 1998, 63: 6535 -
10c
Brummond KM.Kerekes AD.Wan H. J. Org. Chem. 2002, 67: 5156 - 11
Pagenkopf BL.Belanger DB.O’Mahony DJR.Livinghouse T. Synthesis 2000, 1009 - 12 We already reported that iridium-chiral
phosphine complex is an efficient catalyst for highly enantioselective
Pauson-Khand type reaction of enynes:
Shibata T.Takagi K. J. Am. Chem. Soc. 2000, 122: 9852 - Under CO-free conditions, Rh-catalyzed ene-type reaction proceeds to give cross-conjugated trienes:
-
14a
Brummond KM.Chen H.Sill P.You L. J. Am. Chem. Soc. 2002, 124: 15186 -
14b
Shibata T.Takesue Y.Kadowaki S.Takagi K. Synlett 2003, 268
References
A typical experimental procedure is as follows (Table [2] , entry 1): Under an atmosphere of CO (0.2 atm) and Ar (0.8 atm), IrCl(CO)(PPh3)2 (8.2 mg, 1.05 × 10-2 mmol, 5 mol%) was placed in a flask. A degassed xylene solution (5 mL) of allenyne 1a (44.6 mg, 0.210 mmol) was added, and the mixture was the stirred at 120 °C (bath temperature) for 3 h. The solvent was removed under a reduced pressure, and the resulting crude products were purified by thin layer chrom-atography to give pure 2a (40.3 mg, 0.161 mmol, 77%). 4-Methylpenta-2,3-dienyl 3-phenyl-2-propynyl ether (1a). Yellow oil; IR (neat) 2826, 2364, 1448, 1122 cm-1; 1H NMR δ = 1.72 (d, J = 3.0 Hz, 6 H), 4.10 (d, J = 6.6 Hz, 2 H), 4.38 (s, 2 H), 5.04-5.13 (tq, J = 3.0 Hz, 6.6 Hz, 1 H), 7.28-7.32 (m, 3 H), 7.42-7.45 (m, 2 H); 13C NMR δ = 20.3, 57.2, 68.5, 85.1, 85.6, 86.0, 96.1, 122.7, 128.2, 128.3, 131.7, 203.4; HRMS found m/z 212.1209, calcd for C15H16O: 212.1201. 4-Isopropylidene-2-phenyl-7-oxabicyclo[3.3.0]-oct-1-en-3-one (2a). White solid; mp 109-110 °C (hexane); IR (neat) 1686, 1632, 1023 cm-1; 1H NMR δ = 1.94 (s, 3 H), 2.37 (s, 3 H), 3.20 (dd, J = 7.9 Hz, 11.1 Hz, 1H), 3.79-3.85 (m, 1 H), 4.44 (dd, J = 7.9 Hz, 7.9 Hz, 1 H), 4.50 (d, J = 15.4 Hz, 1 H), 4.91 (dd, J = 1.2 Hz, 15.4 Hz, 1 H), 7.25-7.43 (m, 3 H), 7.56-7.58 (m, 2 H); 13C NMR δ = 19.8, 25.2, 47.9, 65.7, 69.7, 128.1, 128.3, 128.4, 130.9, 131.4, 137.5, 148.2, 168.2, 194.6; HRMS found m/z 240.1150, calcd for C16H16O2: 240.1150.