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The target 2-(bicyclo[3.1.0]hex-1-yl)acrylates produced for an ultimate use in low-shrinkage dental composites, must remain colorless even after extended exposure to air and light. They also should have minimal biological activity, e.g. cytotoxity.
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The original protocol was modified (see Experimental Section)
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33750523256
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note
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With this modification even less C-H acidic α-acetylamides can be alkylated.
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19
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0000049821
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Palladium acetate has been applied as a precatalyst for carbonylative transformations of propargyl carbonates. J. Tsuji, T. Mandai, Angew. Chem. 1995, 107, 2830-2854;
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33750519677
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note
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2 is essential. All attempts to perform the bicyclization either under ligand-free conditions, or in the presence of less ligand either failed completely or led to immediate formation of palladium black.
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22
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0034249671
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Trialkyl phosphites are known to be able to reduce palladium(II) to palladium(0), see: I. P. Beletskaya, A. V. Cheprakov, Chem. Rev. 2000, 100, 3009-3066.
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0034127063
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The favorable role of the quaternary ammonium halide most probably is to provide an appropriate concentration of halide ions which help to stabilize the palladium(0) species, see: C. Amatore, A. Jutand, Acc. Chem. Res. 2000, 33, 314-321.
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33750496625
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note
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It is noteworthy, that the use of a tetraalkylammonium iodide causes immediate formation of palladium black.
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25
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20044390256
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33750495396
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note
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An attempted bicyclization of 7g in glacial acetic acid gave only a trace amount (ca. 5%) of the corresponding bicyclic acrylic acid.
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This procedure is also viable for the hydrolysis of ethyl acrylates to give the corresponding acids in excellent yields: V. Bagutski, Dissertation, Universität Göttingen, 2004, p. 77.
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