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A number of hydrophosphonylations, the additions of pentavalent hydrophosphorous compounds, aiming at the synthesis of bidentate ligands, were reported: (a) Stockland, R. A., Jr.; Taylor, R. I.; Thompson, L. E.; Patel, P. B. Org. Lett. 2005, 7, 851-853 and references therein.
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2] would be labile and mat many sorts of copper-phosphide species might be formed upon the addition of cesium carbonate.
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2] would be labile and mat many sorts of copper-phosphide species might be formed upon the addition of cesium carbonate.
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44
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34247156143
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There can be an interaction between the copper and the acetylenic part of 5.
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There can be an interaction between the copper and the acetylenic part of 5.
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45
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34247170808
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31P NMR spectrum of 1a in DMF. The addition of a stoichiometric amount of CuI to the DMF solution furnished a clear homogeneous solution, which exhibited a broad and highly splitting signal at the same chemical shift. The dissolution of CuI indicates the formation of the complex [CuI·1a]. The NMR experiments suggest that the complex would not be robust.
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31P NMR spectrum of 1a in DMF. The addition of a stoichiometric amount of CuI to the DMF solution furnished a clear homogeneous solution, which exhibited a broad and highly splitting signal at the same chemical shift. The dissolution of CuI indicates the formation of the complex [CuI·1a]. The NMR experiments suggest that the complex would not be robust.
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The radical desulfidation of 15 with TTMSS (1.2 equiv to 15) was also successful. However, after several attempts, separation of 15 and silicon-containing residue proved to be problematic in our hands. Small amounts of the corresponding monooxides of 15 were generated during careful chromatographic purification on silica gel for isolation of 15. Purification using a solid phase technique (see the Supporting Information) resulted in unsatisfactory separation of 15 and the silicon-containing residue. We expect that, if the TTMSS-mediated reduction and purification of 15 were performed in a glovebox filled with inert gas, one could isolate 15 in excellent yield
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The radical desulfidation of 15 with TTMSS (1.2 equiv to 15) was also successful. However, after several attempts, separation of 15 and silicon-containing residue proved to be problematic in our hands. Small amounts of the corresponding monooxides of 15 were generated during careful chromatographic purification on silica gel for isolation of 15. Purification using a solid phase technique (see the Supporting Information) resulted in unsatisfactory separation of 15 and the silicon-containing residue. We expect that, if the TTMSS-mediated reduction and purification of 15 were performed in a glovebox filled with inert gas, one could isolate 15 in excellent yield.
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