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Selective propargylic C(sp3)–H activation of methyl-substituted alkynes versus [2 + 2] cycloaddition at a titanium imido template |
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| Authors: | Malte Fischer Manfred Manßen Marc Schmidtmann Thorsten Klüner Rüdiger Beckhaus |
| Institution: | Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR UK.; Anorganische Chemie Universität Tübingen, Auf der Morgenstelle 18, D-72076 Tübingen Germany.; Institut für Chemie, Fakultät für Mathematik und Naturwissenschaften, Carl von Ossietzky Universität Oldenburg, Postfach 2503, D-26111 Oldenburg Germany, |
| Abstract: | The reaction of the titanium imido complex 1b with 2-butyne leads to the formation of the titanium azadiene complex 2a at ambient temperature instead of yielding the archetypical 2 + 2] cycloaddition product (titanaazacyclobutene) which is usually obtained by combining titanium imido complexes and internal alkynes. The formation of 2a is presumably caused by an initial propargylic C(sp3)–H activation step and quantum chemical calculations suggest that the outcome of this unexpected reactivity is thermodynamically favored. The previously reported titanaazacyclobutene I (which is obtained by reacting 1b with 1-phenyl-1-propyne) undergoes a rearrangement reaction at elevated temperature to give the corresponding five-membered titanium azadiene complex 2b.An unexpected reactivity between a titanium imido complex and internal alkynes was unveiled yielding titanaazacyclobutenes instead of the expected 2 + 2] cycloaddition products. |
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