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A Combined Theoretical and Experimental Study of Efficient and Fast Titanocene-Catalyzed 3-exo Cyclizations

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Contribution from the Institut für Theoretische Chemie der Universität zu Köln, Greinstrasse 4, 50939 Köln, Germany, and Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, Gerhard Domagk Strasse 1, 53121 Bonn, Germany
Cite this: J. Am. Chem. Soc. 2005, 127, 19, 7071–7077
Publication Date (Web):April 20, 2005
https://doi.org/10.1021/ja050268w
Copyright © 2005 American Chemical Society
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Abstract

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The mechanism of titanocene mediated 3-exo cyclizations was investigated by a combined theoretical and experimental study. A gradient corrected density functional theory (DFT) method has been scaled against titanocene dichloride, the parent butenyl radical, and in bond dissociation energy (BDE) calculations. The BP86 method using density fitting, and a basis set of triple-ζ quality emerged as a highly reliable tool for studying titanocene mediated radical reactions. The computational results revealed important kinetic and thermodynamic features of cyclopropane formation. Surprisingly, the β-titanoxy radicals, the first intermediates of our investigations, were demonstrated to possess essentially the same thermodynamic stabilization as the corresponding alkyl radicals by comparison of the calculated BDEs. In contrast to suggestions for samarium mediated reactions, the cyclization was shown to be thermodynamically favorable in agreement with earlier kinetic studies. It was established that stereoselectivity of the cyclization is governed by the stability of the intermediates and thus the trans disubstituted products are formed preferentially. The observed ratios of products are in good to excellent agreement with the DFT results. By a combination of computational and experimental results, it was also shown that for the completion of the overall cyclopropane formation the efficiency of the trapping of the cyclopropylcarbinyl radicals is decisive.

*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

†

 Institut für Theoretische Chemie der Universität zu Köln.

‡

 Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn.

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