Synthesis of Tetraarylallenes via Palladium-Catalyzed Addition-Elimination Reactions of 1,1,3-Triaryl-2-propyn-1-ols with Aryl Iodides

Abstract

The palladium-catalyzed reactions of tert-propargylic alcohols with aryl iodides afforded tetraarylallenes in good yields. This reaction involves: (1) oxidative addition of the aryl iodide to Pd(0); (2) arylpalladium intermediate coordination to the carbon-carbon triple bond of the 1,1,3-triaryl-2-propyn-1-ol and subsequent regioselective insertion of the alkynol to form β-hydroxyvinylpalladium species; and (3) β-elimination to produce the tetraarylallenes. Generally, the best results are obtained by employing 5 mol% of Pd(TFA)₂, 10 mol% of PPh₃, two equivalents of aryl iodide and five equivalents of Et₃N in MeCN.

palladium - tetraarylallenes - addition-elimination - 1,1,3-triaryl-2-propyn-1-ol

References

<A NAME="RU10905ST-1A">1a</A> Brandsma L. Verkruijsse HD. Synthesis of Acetylenes, Allenes, and Cumulenes   Elsevier; Amsterdam: 1981. 

<A NAME="RU10905ST-1B">1b</A> The Chemistry of Allenes   Landor SR. Academic Press; London: 1982. 

<A NAME="RU10905ST-1C">1c</A> Schuster HF. Coppola GM. Allenes in Organic Synthesis   Wiley; New York: 1984. 

<A NAME="RU10905ST-1D">1d</A> Pasto DJS. Tetrahedron  1984,  40:  2805 

<A NAME="RU10905ST-1E">1e</A> Hoffmann-Roder A. Krause N. Angew. Chem. Int. Ed.  2002,  41:  2933 

For reviews, see:

<A NAME="RU10905ST-2A">2a</A> Marshall JA. Chem. Rev.  1996,  96:  31 

<A NAME="RU10905ST-2B">2b</A> Yamamoto Y. Radhakrishnanan U. Chem. Soc. Rev.  1999,  28:  199 

<A NAME="RU10905ST-2C">2c</A> Zimmer R. Dinesh CU. Nandanam E. Khan FA. Chem. Rev.  2000,  100:  3067 

<A NAME="RU10905ST-2D">2d</A> Marshall JA. Chem. Rev.  2000,  100:  3163 

<A NAME="RU10905ST-3A">3a</A> Yamamoto Y. Al-Masum M. Asao N. J. Am. Chem. Soc.  1994,  116:  6019 

<A NAME="RU10905ST-3B">3b</A> Trost BM. Gerusz VJ. J. Am. Chem. Soc.  1995,  117:  5156 

<A NAME="RU10905ST-3C">3c</A> Franzen J. Lofstedt J. Dorange I. Backvall J.-E. J. Am. Chem. Soc.  2002,  124:  11246 

<A NAME="RU10905ST-4A">4a</A> Chang H.-M. Cheng C.-H. Org. Lett.  2000,  2:  3439 

<A NAME="RU10905ST-4B">4b</A> Anwar U. Grigg R. Rasparini M. Savic V. Sridharan V. Chem. Commun.  2000,  645 

<A NAME="RU10905ST-5A">5a</A> Wender PA. Jenkins TE. Suzuki S. J. Am. Chem. Soc.  1995,  117:  1843 

<A NAME="RU10905ST-5B">5b</A> Kimura M. Horino Y. Wakamiya Y. Okajima T. Tamaru Y. J. Am. Chem. Soc.  1997,  119:  10869 

<A NAME="RU10905ST-5C">5c</A> Shanmugasundaram M. Wu M.-S. Jeganmohan M. Huang C.-W. Cheng C.-H. J. Org. Chem.  2002,  67:  7724 

<A NAME="RU10905ST-6A">6a</A> Yang F.-Y. Wu M.-Y. Cheng C.-H. J. Am. Chem. Soc.  2000,  122:  7122 

<A NAME="RU10905ST-6B">6b</A> Tsuji J. Shimizu I. Chem. Lett.  1984,  233 

<A NAME="RU10905ST-6C">6c</A> Chaptal N. Colovray-Gotteland V. Grandjean C. Cazes B. Gore J. Tetrahedron Lett.  1991,  32:  1795 

<A NAME="RU10905ST-7">7</A> Takagi K. Tomita I. Endo T. Macromolecules  1997,  30:  7386 

<A NAME="RU10905ST-8A">8a</A> Jarvi ET. McCarthy JR. Nucleosides Nucleotides  1994,  13:  585 

<A NAME="RU10905ST-8B">8b</A> Dauvergne J. Burger A. Biellmann J.-F. Nucleosides, Nucleotides Nucleic Acids  2001,  20:  1775 

<A NAME="RU10905ST-9A">9a</A> Alexakis A. Marek I. Mangeney P. Normant JF. Tetrahedron  1991,  47:  1677 

<A NAME="RU10905ST-9B">9b</A> Nantz MH. Bender DM. Janaki S. Synthesis  1993,  577 

<A NAME="RU10905ST-10">10</A> Tanaka K. Otsubo K. Fuji K. Synlett  1995,  933 

<A NAME="RU10905ST-11">11</A> Doering WE. LaFlamme PM. Tetrahedron  1958,  2:  75 

<A NAME="RU10905ST-12">12</A> Brummond KM. Dingess EA. Kent JL. J. Org. Chem.  1996,  61:  6096 

<A NAME="RU10905ST-13">13</A> Delouvrie B. Lacote E. Fensterbank L. Malacria M. Tetrahedron Lett.  1999,  40:  3565 

<A NAME="RU10905ST-14A">14a</A> Mizuno M. Fuji K. Tomioka K. Angew. Chem. Int. Ed.  1998,  37:  515 

<A NAME="RU10905ST-14B">14b</A> Nagaoka Y. Tomioka K. Org. Lett.  1999,  1:  1467 

<A NAME="RU10905ST-14C">14c</A> Inoue H. Tsubouchi H. Nagaoka Y. Tomioka K. Tetrahedron Lett.  2002,  58:  83 

<A NAME="RU10905ST-15A">15a</A> Tsuji J. Sugiura T. Minami I. J. Chem. Soc., Chem. Commun.  1986,  922 

<A NAME="RU10905ST-15B">15b</A> Tsuji J. Sugiura T. Yuhara M. Minami I. Synthesis  1987,  603 

<A NAME="RU10905ST-16A">16a</A> Badone D. Cardamone R. Guzzi U. Tetrahedron Lett.  1994,  35:  5477 

<A NAME="RU10905ST-16B">16b</A> Huang C.-W. Shanmugasundaram M. Chang H.-M. Cheng C.-H. Tetrahedron Lett.  2003,  59:  3635 

<A NAME="RU10905ST-17A">17a</A> Ma S. Zhang A. J. Org. Chem.  1998,  63:  9601 

<A NAME="RU10905ST-17B">17b</A> Ma S. Zhang A. Yu Y. Xia W. J. Org. Chem.  2000,  65:  2287 

<A NAME="RU10905ST-17C">17c</A> Ma S. He Q. Angew. Chem. Int. Ed.  2004,  43:  988 

<A NAME="RU10905ST-18A">18a</A> Lee K. Seomon D. Lee PH. Angew. Chem. Int. Ed.  2002,  41:  3901 

<A NAME="RU10905ST-18B">18b</A> Lin M.-J. Loh T.-P. J. Am. Chem. Soc.  2003,  125:  13042 

<A NAME="RU10905ST-19A">19a</A> Ogasawara M. Ikeda H. Hayashi T. Angew. Chem. Int. Ed.  2000,  39:  1042 

<A NAME="RU10905ST-19B">19b</A> Ogasawara M. Ge Y. Uetake K. Fan L. Takahashi T. J. Org. Chem.  2005,  70:  3871 

<A NAME="RU10905ST-20A">20a</A> Nakamura H. Kamakura T. Ishikura M. Biellmann J.-F. J. Am. Chem. Soc.  2004,  126:  5958 

<A NAME="RU10905ST-20B">20b</A> Nakamura H. Kamakura T. Onagi S. J. Org. Chem.  2005,  70:  2357 

<A NAME="RU10905ST-21A">21a</A> Alexakis A. Marek I. Mangeney P. Normant JF. J. Am. Chem. Soc.  1990,  112:  8042 

<A NAME="RU10905ST-21B">21b</A> Ogoshi S. Nishiguchi S. Tsutsumi K. Kurosawa H. J. Org. Chem.  1995,  60:  4650 

<A NAME="RU10905ST-21C">21c</A> Sturla SJ. Kablaoui NM. Buchwald SL. J. Am. Chem. Soc.  1999,  121:  1976 

<A NAME="RU10905ST-22">22</A> Wu M.-J. Wei L.-M. Lin C.-F. Leou S.-P. Wei L.-L. Tetrahedron  2001,  57:  7839 

<A NAME="RU10905ST-23">23</A>

Crystal data for 3aa: C₂₇H₂₀, M = 344.43 g/mol, crystal size: 0.50 × 0.50 × 0.50 mm, monoclinic, space group P2₁/c, λ = 0.71073 Å, a = 12.1405 (1) Å, b = 8.4186 (1) Å, c = 19.2201 (2) Å, α = 90°, β = 101.0624 (5)°, γ = 90°, V = 1927.91 (3) ų, Z = 4, D = 1.187 mg/m³, µ = 0.067
mm^-1, T = 295 (2) K, θ range: 1.71-27.50°, reflections collected: 17949, independent reflections: 4403 (R _int = 0.0313), refinement method: full-matrix least-squares on F², final R values [I > 2σ(I)]: R ₁ = 0.0516, wR ₂ = 0.1300. Diffractometer: NONIUS KappaCCD. Crystallographic data (excluding structure factors) for this structure have been deposited at the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 260843, and may be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1ED, UK [fax: [phone];
e-mail [e-mail]].

<A NAME="RU10905ST-24A">24a</A> Wei L.-L. Wei L.-M. Pan W.-B. Wu M.-J. Synlett  2004,  1497 

<A NAME="RU10905ST-24B">24b</A> Lin C.-F. Lu W.-D. Wang I.-W. Wu M.-J. Synlett  2003,  2057 

<A NAME="RU10905ST-24C">24c</A> Wei L.-M. Lin C.-F. Wu M.-J. Tetrahedron Lett.  2000,  41:  1215 

<A NAME="RU10905ST-24D">24d</A> Wei L.-L. Wei L.-M. Pan W.-B. Leou S.-P. Wu M.-J. Tetrahedron Lett.  2003,  44:  1979 

<A NAME="RU10905ST-24E">24e</A> Wei L.-M. Wei L.-L. Pan W.-B. Wu M.-J. Tetrahedron Lett.  2003,  44:  595