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Updated: Jul 23, 2026
Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts
Published on: February 24, 2015
New Routes to Synthetically Useful, Sterically Encumbered Arylaluminum Halides and Hydride Halides
Rudolf J. Wehmschulte1, Philip P. Power
1Department of Chemistry, University of California, Davis, California 95616.
Abstract:
The synthesis and structural characterization of the compounds MesAlCl(2)(THF) (1), MesAlCl(2) (2), MesAl(H)Cl(THF) (3a), MesAl(H)Cl (4a), and (MesAlH(2))(2) (5) (Mes = 2,4,6-t-Bu(3)C(6)H(2)(-)) are described as well as those for two compounds 3b and 4b that are analogs of 3a and 4a but have H:Cl ratios that are less than 1:1. All compounds were characterized by (1)H, (13)C NMR, and IR spectroscopy, and 1, 2, 3a, and 4b were additionally characterized by X-ray crystallography. Compound 1 is best synthesized by the reaction of [(THF)(2)LiH(3)AlMes](2) (6) with 6 equiv of Me(3)SiCl. A more conventional route involving the addition of (THF)(2)LiMes to 2 equiv of AlCl(3) in toluene usually affords a mixture of 1 and AlCl(3).THF. Recrystallization of 1 from n-hexane results in a species that has less than 1 equiv of THF per MesAlCl(2). The THF free complex 2 may be obtained in quantitative yield by heating 1 for 20 min at 90 degrees C under reduced pressure. Compound 3a may be obtained by treating a 1:1 mixture of MesLi(THF)(2) and LiAlH(4) with 2 equiv of Me(3)SiCl or by the addition of slightly less than 4 equiv of Me(3)SiCl to 6. The THF can be removed from 3a by sublimation to give 4a. The related compounds 3b and 4b, which display an aluminum-bound H:Cl ratio that is deficient in H, can be obtained by reactions with slightly more than 2 equiv of Me(3)SiCl. Crystal data at 130 K with Cu Kalpha (lambda = 1.541 78 Å) radiation: 1, C(22)H(37)AlCl(2)O, a = 11.889(3) Å, b = 9.992(3) Å, c = 19.704(5) Å, orthorhombic, space group Pca2(1), Z = 4, R = 0.068 for 1556 (I > 2sigma(I)) data; 2, C(18)H(29)AlCl(2), a = 12.147(5) Å, b = 18.042(6) Å, c = 17.771(7) Å, beta = 95.77(3) degrees, monoclinic, space group P2(1)/n,Z = 8, R = 0.032 for 4610 (I > 2sigma(I)) data; 3a, C(22)H(38)AlClO, a = 16.887(7) Å, b = 16.333(6) Å, c = 8.739(3) Å, beta = 101.41(3) degrees, monoclinic, space group P2(1)/c, Z = 4, R = 0.073 for 2752 (I > 2sigma(I)) data; 4b, C(18)H(29.64)AlCl(1.36), a = 12.077(3) Å, b = 17.920(3) Å, c = 17.634(5) Å; beta = 95.21(2) Å, monoclinic, space group P2(1)/n,Z = 8, R = 0.070 for 4261 (I > 2sigma(I)) data.
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