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DOI: 10.1055/s-2005-872241
Palladium-Catalyzed Novel Cycloisomerization: An Unprecedented Domino Oxidative Cyclization towards Substituted Carbocycles
Publication History
Publication Date:
22 July 2005 (online)
Abstract
Efficient Pd-catalyzed cyclization of homoallylated β-bromo-vinylalcohols via a domino process to carbocycle derivatives in presence of different bases is reported. An unexpected and novel palladium-mediated Heck-type intramolecular oxidative cyclization of 1-bromohexa-1-ene-5-yn-3-ol derivatives is also described.
Key words
Heck reaction - palladacycles - tandem reactions - oxidation - isomerization
-
1a
Nakamura I.Yamamoto Y. Chem. Rev. 2004, 104: 2127 -
1b
Tsuji J. Transition Metal Reagents and Catalysts: Innovations in Organic Synthesis Wiley; New York: 2002. -
1c
Minami I.Yuhara M.Watanabe H.Tsuji J. J. Organomet. Chem. 1987, 334: 225 ; and references cited therein -
2a
Zeni G.Larock RC. Chem. Rev. 2004, 104: 2285 -
2b
Widenhoefer RA. Acc. Chem. Res. 2002, 35: 905 -
2c
Tan Z.Negishi E.-i. Handbook of Organopalladium Chemistry for Organic Synthesis Vol 1: John Wiley and Sons; New York: 2002. p.863-942 -
3a
Muzart J. Tetrahedron 2003, 59: 5789 -
3b
Gibson SE.Jones JO.Kalindjian SB.Knight JD.Mainolfi N.Rudd M.Steed JW.Tozer MJ.Wright PT. Tetrahedron 2004, 60: 6945 -
3c
Tobrman T.Dvorak D. Tetrahedron Lett. 2004, 45: 273 -
3d
Arcadi A.Bernocchi E.Cacchi S.Marinell F.Scarinci A. Synlett 1991, 177 -
3e
Ganchegui B.Bouquillon S.Henin F.Muzart J. J. Mol. Catal. A: Chem. 2004, 214: 65 -
3f
Wavrin L.Nicolas C.Viala J.Rodriguez J. Synlett 2004, 1820 -
4a
Trost BM.Dumas J.Villa M. J. Am. Chem. Soc. 1992, 114: 9836 -
4b
Danishefsky SJ.Masters JJ.Young WB.Link JT.Snyder LB.Magee TV.Jung DK.Isaacs RCA.Bornmann WG.Alaimo CA.Coburn CA.Di Grandi MJ. J. Am. Chem. Soc. 1996, 118: 2843 -
4c
Hong CY.Kado N.Overman LE. J. Am. Chem. Soc. 1993, 115: 11028 -
4d
Tietze LF.Evers H.Topken E. Angew. Chem. Int. Ed. 2001, 40: 903 -
4e
Nicolaou KC.Gray DLF.Tae J. J. Am. Chem. Soc. 2004, 126: 613 -
4f
Willmore ND.Goodman R.Lee HH.Kennedy RM. J. Org. Chem. 1992, 57: 1216 -
5a
Belestkaya IP.Chheprakov AV. Chem. Rev. 2000, 100: 3009 -
5b
Grigg R.Millington EL.Thornton-Pett M. Tetrahedron Lett. 2002, 43: 2605 -
5c
Oestreich M.Dennison PR.Kodanko JJ.Overman LE. Angew. Chem. Int. Ed. 2001, 40: 1439 -
5d
Balme G.Bouyssi D.Lomberget T.Monteiro N. Synthesis 2003, 2115 -
5e
Link J. Org. React. 2002, 60: 157 -
5f
Smith AB.Jerris PJ. J. Am. Chem. Soc. 1981, 103: 194 - 6
Mal SK.Ray D.Ray JK. Tetrahedron Lett. 2004, 45: 277 -
9a
Burns B.Grigg R.Sridharan V.Worakun T. Tetrahedron Lett. 1988, 29: 4325 -
9b
Nuss JM.Levine BH.Rennels RA.Heravi MM. Tetrahedron Lett. 1991, 32: 5243 - For mechanistic studies on palladium-catalyzed transformations using phosphine ligands see:
- 10a Alcazar Roman L. M., Hartwig J. F.; Organometallics; 2002, 21: 491
- 10b Roy A. H., Hartwig J. F.; J. Am. Chem. Soc.; 2001, 123: 1232
-
10c
Alcazar Roman LM.Hartwig JF.Rheingold AL.Liable-Sands LM.Guzei IA. J. Am. Chem. Soc. 2000, 122: 4618 -
10d
Elsevier CJ.Kleijn H.Boersma J.Vermeer P. Organometallics 1986, 5: 716 -
10e
Wojcicki A. New J. Chem. 1994, 18: 61 -
10f
Kurosawa H.Ogoshi S. Bull. Chem. Soc. Jpn. 1998, 71: 973 -
10g
Casey CP.Boller TM.Kraft S.Guzei IA. J. Am. Chem. Soc. 2002, 124: 13215 -
10h
Tsutsumi K.Ogoshi S.Nishiguchi S.Kurosawa H. J. Am. Chem. Soc. 1998, 120: 1938 -
10i
Baize MW.Blosser PW.Plantevin V.Schimpff DG.Gallucci JC.Wojcicki A. Organometallics 1996, 15: 164 -
10j
Casey CP.Nash JR.Yi CS.Selmeczy AD.Chung S.Powell DR.Hayashi RK. J. Am. Chem. Soc. 1998, 120: 722
References
General Procedure for the Palladium-Catalyzed Cyclization. The appropriate homoallylated or propargylated β-bromo-vinylalcohols, Pd(OAc)2 (10 mol%), PPh3 (0.25 equiv), base (1 equiv)[HCOONa (1 equiv) for propargylated compound only] and DMF (6-8 mL) were placed in a two-neck round-bottom flask. After degassing with N2 the mixture was heated to 70 °C for 4 h. After cooling, the reaction mixture was diluted with cold H2O and extracted with Et2O (4 × 25 mL), and dried (Na2SO4). The solvent was evaporated, and the product was isolated by column chromatography (PE-EtOAc 9:1).
8
General Procedure for Propargylation.
A mixture of β-bromo vinylaldehyde (1 mmol), propargyl bromide (1.3 mmol), indium metal (SRL, India) (1.2 mmol), NaI (3 mmol) in DMF (4-5 mL) was stirred at 0 °C until completion of the reaction (checked by TLC). The reaction mixture was quenched with aq NH4Cl solution diluted with H2O and extracted with Et2O (3 × 25 mL). The solvent was removed at r.t. under vacuum.
Spectral Data of Representative Compounds.
7-Methoxy-9-methylene-8,9-dihydro-7
H
-cyclopenta[
a
]acenaphthylene (II):
1H NMR (200 MHz, C6D6): δ = 3.01-3.16 (m, 2 H), 3.20 (s, 3 H), 4.48 (dd, 1 H, J = 2.87 Hz, J = 2.96 Hz), 5.02 (br s, 1 H), 5.49 (br s, 1 H), 7.20-7.31 (m, 3 H), 7.45-7.60 (m, 3 H). Anal Calcd for C17H14O: C, 87.15; H, 6.02. Found: C, 88.25; H, 5.92.
3-Methyl-3,4,5,6,7,8-hexahydro-2
H
-azulen-1-one (
3d):
IR (CHCl3): νmax = 1685 cm-1. 1H NMR (200 MHz, CDCl3): δ = 1.15 (d, 3 H, J = 6.96 Hz), 1.42-1.67 (m, 6 H), 1.73-1.83 (m, 4 H), 2.26-2.58 (m, 2 H), 2.67-2.7 (m, 1 H). 13C NMR (75 MHz, CDCl3): δ = 18.98, 23,09, 26.33, 26.50, 31.13, 31.42, 37.04, 43.13, 141.72, 181.02, 208.11. MS (EI, 70 eV): m/z = 164 [M+]. Anal Calcd for C11H16O: C, 80.44; H, 9.82. Found: C, 80.65; H, 9.62.
10-Methyl-9,10-dihydro-8
H
-fluoranthen-7-one (
6b):
IR (CHCl3): νmax = 1660 cm-1. 1H NMR (200 MHz, CDCl3): δ = 1.55 (d, 3 H, J = 7.12 Hz), 2.06-2.09 (m, 1 H), 2.39-2.78 (m, 3 H), 3.39-3.45 (m, 1 H), 7.53 (m, 2 H), 7.79 (d, 1 H, J = 8.20 Hz), 7.92-7.98 (m, 2 H), 8.26 (d, 1 H, J = 6.79 Hz). 13C NMR (75 MHz, CDCl3): δ = 20.38, 29.19, 31.32, 35.68, 126.11, 126.21, 126.96, 127.54, 128.41, 128.66, 130.86, 136.81, 161.66, 196.89. MS (EI, 70 eV): m/z = 234 [M+]. Anal Calcd for C17H14O: C, 87.15; H, 6.02. Found: C, 86.92; H, 5.93.