An interesting regioselectivity is observed when the mixture of potassium crotyltrifluoroborate ( 1a ) and aroyl chlorides having electron-deficient and electron-rich groups is microwaved in the presence of palladium-catalyst. In the case of electron withdrawing group with phenyl ring of aroyl chlorides, isomerized α , β -unsaturated compound 3 is the product whereas electron donating group with phenyl ring of aroyl chlorides furnishes α -adduct 4 . Similar aroylation reaction is also established for potassium allyltrifluoroborate ( 1b ). In this case, regioselectivity is unaffected with changing electron-rich or electron-deficient groups in phenyl ring of the aroyl chlorides. Reactions proceed with, essentially in same rate, affording the corresponding aryl propenyl ketones (crotonophenones) 5 in good to high yields.
Marshall, J.A. (2000) Synthesis and Reactions of Allylic, Allenic, Vinylic, and Arylmetal Reagents from Halides and Esters via Transient Organopalladium Intermediates. Chemical Reviews, 100, 3163-3185. https://doi.org/10.1021/cr000003u
Stille, J.K. (1985) In: Hartley, F.R. and Patai, S., Eds., The Chemistry of the Metal-Carbon, Vol. 2, John Wiley, New York, 625.
Sakurai, H. and Hosomi, A. (1977) Chemistry of Organosilicon Compounds. 99. Conjugate Addition of Allylsilanes to .Alpha.,.Beta.-Enones. A New Method of Stereoselective Introduction of the Angular Allyl Group in Fused Cyclic .Alpha.,.Beta.-Enones. Journal of the American Chemical Society, 99, 1673-1675. https://doi.org/10.1021/ja00447a080
Yanagisawa, A., Hibino, H., Nomura, N. and Yamamoto, H. (1993) Unprecedented Gamma-Selective Nucleophilic Substitution Reaction of Allylmetal Reagents: A New Cross-Coupling of Diphenyl Phosphates with Allylic Grignard Reagents. Journal of the American Chemical Society, 115, 5879-5880. https://doi.org/10.1021/ja00066a088
Corey, E.J., Semmelhack, M.F. and Hegedus, L.S. (1968) The Course of Allylic Coupling Reactions Involving Allylnickel Complexes. Journal of the American Chemical Society, 90, 2416-2417. https://doi.org/10.1021/ja01011a035
Hirai, A., Nakamura, M. and Nakamura, E. (2000) Mechanism of Addition of Allylmetal to Vinylmetal. Dichotomy between Metallo-Ene Reaction and Metalla-Claisen Rearrangement. Journal of the American Chemical Society, 122, 11791-11798. https://doi.org/10.1021/ja002563g
Trost, B.M. and Vranken, D.L.V. (1996) Asymmetric Transition Metal-Catalyzed Allylic Alkylations. Chemical Reviews, 96, 395.
Yamamoto, Y. and Asao, N. (1993) Selective Reactions Using Allylic metals. Chemical Reviews, 93, 2207.
Al-Masum, M. and Liu, K.-Y. (2011) A New Organic Transformation by Introducing Crotyl/Allyltrifluoroborates in Cross-Coupling Reaction with Aroyl Chlorides. Tetrahedron Letters, 52, 5090-5093.
Lautens, M. and Maddess, M.L. (2004) Chemoselective Cross Metathesis of Bishomoallylic Alcohols:Rapid Access to Fragment A of the Cryptophycins. Organic Letters, 6, 1883-1886.
Nowrouzi, F., Janetzko, J. and Batey, R.A. (2010) Indium-Promoted Chemo- and Diastereoselective Allylation of α,β-Epoxy Ketones with Potassium Allyltrifluoroborate. Organic Letters, 12, 5490-5493. https://doi.org/10.1021/ol1023757
Thadani, A.N. and Batey, R.A. (2002) A Mild Protocol for Allylation and Highly Diastereoselective Syn or Anti Crotylation of Aldehydes in Biphasic and Aqueous Media Utilizing Potassium Allyl- and Crotyltrifluoroborates. Organic Letters, 4, 3827-3830. https://doi.org/10.1021/ol026619i
Solin, N., Wallner, O.A. and Szabo, K.J. (2005) Palladium Pincer-Complex Catalyzed Allylation of Tosylimines by Potassium Trifluoro(Allyl)Borates. Organic Letters, 7, 689-691. https://doi.org/10.1021/ol0475010
Nakamura, H. and Shimizu, K. (2011) Catalytic Reactions of Bis-π-Allylpalladium Generated from Allyltrifluoroborate. Tetrahedron Letters, 52, 426-429. https://doi.org/10.1016/j.tetlet.2010.11.082
Al-Masum, M. and Alam, S. (2009) Remarkable Regioselectivity in Microwave-Enhanced Palladium-Catalyzed Allylation Reaction Involving Allyltrifluoroborates and Aryl Halides. Tetrahedron Letters, 50, 5201-5204. https://doi.org/10.1016/j.tetlet.2009.06.134
Yamamoto, Y., Takada, S. and Miyaura, N. (2006) Γ-Selective Cross-Coupling of Potassium Allyltrifluoroborates with Aryl and 1-Alkenyl Bromides Catalyzed by a Pd(OAc)2/D-t-BPF Complex. Chemistry Letters, 35, 704-705. https://doi.org/10.1246/cl.2006.704
Sebelius, S., Olsson, V.J., Wallner, O.A. and Szabo, K.J. (2006) Palladium-Catalyzed Coupling of Allylboronic Acids with Iodobenzenes. Selective Formation of the Branched Allylic Product in the Absence of Directing Groups. Journal of the American Chemical Society, 128, 8150-8151. https://doi.org/10.1021/ja062585o
Molander, G.A. and Ham, J. (2006) Synthesis of Functionalized Organotrifluoroborates via Halomethyltrifluoroborates. Organic Letters, 8, 2031-2034. https://doi.org/10.1021/ol060375a
Molander, G.A. and Figueroa, R. (2005) Organotrifluoroborates: Expanding Organoboron Chemistry. Aldrichchimica Acta, 38, 49-56.
Molander, G.A. and Felix, L.A. (2005) Stereoselective Suzuki-Miyaura Cross-Coupling Reactions of Potassium Alkenyltrifluoroborates with Alkenyl Bromides. Journal of Organic Chemistry, 70, 3950-3956. https://doi.org/10.1021/jo050286w
Tremblay-Morin, J-P., Raeppel, S. and Gaudette, F. (2004) Lewis Acid-Catalyzed Mannich type Reactions with Potassium Organotrifluoroborates. Tetrahedron Letters, 45, 3471-3474. https://doi.org/10.1016/j.tetlet.2004.03.014
Molander, G.A. and Ribagorda, M. (2003) Expanding Organoboron Chemistry:Epoxidation of Potassium Organotrifluoroborates. Journal of the American Chemical Society, 125, 11148-11149. https://doi.org/10.1021/ja0351140
Quach, T.D. and Batey, R.A. (2003) Copper(II)-Catalyzed Ether Synthesis from Aliphatic Alcohols and Potassium Organotrifluoroborate Salts. Organic Letters, 5, 1381-1384. https://doi.org/10.1021/ol034454n
Molander, G.A. and Bernardi, C.R. (2002) Suzuki-Miyaura Cross-Coupling Reactions of Potassium Alkenyltrifluoroborates. Journal of Organic Chemistry, 67, 8424-8429. https://doi.org/10.1021/jo026236y
Molander, G.A., Katona, B.W. and Machrouhi, F. (2002) Development of the Suzuki-Miyaura Cross-Coupling Reaction:Use of Air-Stable Potassium Alkynyltrifluoroborates in Aryl Alkynylations. Journal of Organic Chemistry, 67, 8416-8423. https://doi.org/10.1021/jo0262356
Pucheault, M., Darses, S. and Genet, J.-P. (2002) Potassium Organotrifluoroborates in Rhodium-Catalyzed Asymmetric 1,4-Additions to Enones. European Journal of Organic Chemistry, 2002, 3552-3557. https://doi.org/10.1002/1099-0690(200211)2002:21 :AID-EJOC3552>3.0.CO;2-4
Molander, G.A. and Rivero, M.R. (2002) Suzuki Cross-Coupling Reactions of Potassium Alkenyltrifluoroborates. Organic Letters, 4, 107-109. https://doi.org/10.1021/ol0169729
Batey, R.A., Thadani, A.N., Smil, D.V. and Lough, A. (2000) Diastereoselective Allylation and Crotylation Reactions of Aldehydes with Potassium Allyl- and Crotyltrifluoroborates under Lewis Acid Catalysis. Synthesis, 2000, 990-998. https://doi.org/10.1055/s-2000-6303
Darses, S., Michauld, G. and Genet, J.-P. (1999) Potassium Organotrifluoroborates: New Partners in Palladium-Catalysed Cross-Coupling Reactions. European Journal of Organic Chemistry, 1999, 1875-1883. https://doi.org/10.1002/(SICI)1099-0690(199908)1999:8 :AID-EJOC1875>3.0.CO;2-W
Darses, S. and Genet, J.-P. (2008) Potassium Organotrifluoroborates:New Perspectives in Organic Synthesis. Chemical Reviews, 108, 288-325. https://doi.org/10.1021/cr0509758
Mann, G., Shelby, Q., Roy, A.H. and Hartwig, J. (2003) Electronic and Steric Effects on the Reductive Elimination of Diaryl Ethers from Palladium(II). Organometallics, 22, 2775-2789. https://doi.org/10.1021/om030230x
Elsagir, A.R., Gassner, F., Gorls, H. and Dinjus, E. (2000) Bidentate Ferrocenylphosphines and Their Palladium(II)Dichloride Complexes—X-Ray Structural and NMR Spectroscopic Investigations and First Results of Their Characteristics in the Pd-Catalysed Cooligomerisation of 1,3-Butadiene with CO2. Journal of Organometallic Chemistry, 597, 139-145. https://doi.org/10.1016/S0022-328X(99)00670-1
Bianchini, C., Meli, A., Overhauser, W., Parisel, S., Passaglia, E., Ciardelli, F., Gusev, O.V., Kal’sin, A.M. and Vologdin, N. (2005) Ethylene Carbonylation in Methanol and in Aqueous Media by Palladium(II) Catalysts Modified with 1,1‘-Bis(Dialkylphosphino)Ferrocenes. Organometallics, 24, 1018-1030. https://doi.org/10.1021/om049109w
Grasa, G.A. and Colacot, T.J. (2007) Α-Arylation of Ketones Using Highly Active, Air-Stable (DtBPF)PdX2(X = Cl, Br) Catalysts. Organic Letters, 9, 5489-5492. https://doi.org/10.1021/ol702430a
Al-Masum, M., Ng, E. and Wai, M.C. (2011) Palladium-Catalyzed Direct Cross-Coupling of Potassium Styryltrifluoroborates and Benzoyl Chlorides—A One Step Method for Chalcone Synthesis. Tetrahedron Letters, 52, 1008-1010. https://doi.org/10.1016/j.tetlet.2010.12.085
Labadie, J.W. and Stille, J.K. (1983) Mechanisms of the Palladium-Catalyzed Couplings of Acid Chlorides with Organotin Reagents. Journal of the American Chemical Society, 105, 6129-6137. https://doi.org/10.1021/ja00357a026
Milstein, D. and Stille, J.K. (1978) A General, Selective, and Facile Method for Ketone Synthesis from Acid Chlorides and Organotin Compounds Catalyzed by Palladium. Journal of the American Chemical Society, 100, 3636-3638. https://doi.org/10.1021/ja00479a077
Urawa, Y. and Ogura, K. (2003) A Convenient Method for Preparing Aromatic Ketones from Acyl Chlorides and Arylboronic Acids via Suzuki-Miyaura Type Coupling Reaction. Tetrahedron Letters, 44, 271-273. https://doi.org/10.1016/S0040-4039(02)02501-7
Haddach, M. and McCarthy, J.R. (1999) A New Method for the Synthesis of Ketones: The Palladium-Catalyzed Cross-Coupling of Acid Chlorides with Arylboronic Acid. Tetrahedron Letters, 40, 3109-3112. https://doi.org/10.1016/S0040-4039(99)00476-1
Bumagin, N., Korolev, D.N., Bumagin, N. and Korolev, D.N. (1999) Synthesis of Unsymmetric Ketones via Ligandless Pd-Catalyzed Reaction of Acyl Chlorides with Organoboranes. Tetrahedron Letters, 40, 3057-3060. https://doi.org/10.1016/S0040-4039(99)00364-0
Xin, B., Zhang, Y. and Cheng, K. (2007) The Surfactant-Promoted Cross-Coupling Reactions of Arylboronic Acids with Carboxylic Anhydrides or Acyl Chlorides in Water. Synthesis, 2007, 1970-1978. https://doi.org/10.1055/s-2007-983729
Hegedus, L.S., Darlington, W.H. and Russell, C.E. (1980) Cyclopropanation of Ester Enolates by .Pi-Allylpalladium Chloride Complexes. Journal of Organic Chemistry, 45, 5193-5196. https://doi.org/10.1021/jo01313a034