Hydrofunctionalisation of an Aromatic Triphosphabenzene |
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Authors: | Dr. Rosalyn L. Falconer Dihao Zeng Prof. Michael Green Prof. Douglas W. Stephan Prof. John E. McGrady Dr. Christopher A. Russell |
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Affiliation: | 1. School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS UK;2. Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QZ UK;3. Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6 Canada |
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Abstract: | The aromatic heterocycle 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene reacts with a series of silanes, germanes and stannanes, with weaker E−H bonds reacting in an increasingly facile manner. All react by 1,4-addition to give bicyclic products with diastereomeric ratios varying with the substrate. Density functional theory (DFT) calculations show that activation of the E−H bond occurs across the 1,4-C/P axis of the triphosphabenzene, with the small energetic differences with respect to the stereochemistry of the addition offering insight into the experimentally observed diastereomeric ratios. |
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Keywords: | hydrofunctionalisation hydrosilylation metal-free synthesis phosphorus triphosphabenzene |
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