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Carbonyl Coupling Reactions Catalytic in Titanium and the Use of Commercial Titanium Powder for Organic Synthesis

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http://pubman.mpdl.mpg.de/cone/persons/resource/persons58380

Fürstner,  Alois
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons132879

Hupperts,  Achim
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Fürstner, A., & Hupperts, A. (1995). Carbonyl Coupling Reactions Catalytic in Titanium and the Use of Commercial Titanium Powder for Organic Synthesis. Journal of the American Chemical Society, 117(16), 4468-4475. doi:10.1021/ja00121a004.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0014-A47C-2
Abstract
The high thermodynamic stability of titanium oxides formed as the inorganic byproducts in McMurrytype reactions has so far prevented the development of a catalytic procedure for such reductive carbonyl coupling processes. Similarly, a tightly bound oxide layer passivates the surface of commercial titanium, which is unreactive toward organic substrates under conventional conditions. This paper outlines a way to overcome both of these problems. Thus, oxoamides 1a-h can be reductively cyclized to indoles 2a-h using only catalytic amounts of low-valent titanium if the reaction is carried out in the presence of a chlorosilane. Specifically, the method is based upon the in situ generation of an activated titanium species from TiCl3 and Zn in the presence of the substrate, followed by regeneration of titanium chloride from the titanium oxides formed via ligand exchange with the admixed chlorosilane. Its proper choice is crucial for obtaining both good turnover numbers and clean conversions. Depending on the product structure, (TMS)Cl, ClMe2SiCH2CH2SiMe2Cl (5), or ClMe2Si(CH2)3CN (6) was found to be best suited. Similarly, chlorosilanes also effect the activation of commercial titanium powder which may then be used as a performant off-the-shelf reagent for various types of carbonyl and acetal coupling reactions, for the deoxygenation of epoxides and for the reductive cyclization of oxoamides or oxoesters to indoles, benzofurans, and 2-quinolones. Under these conditions retinal can be reductively dimerized to ß-carotene in good yield. Moreover, the titanium/chlorosilane reagent combination exhibits a strong template effect, allowing macrocyclization reactions without recourse to high dilution. Up to 36-membered rings have been closed in that way. 29Si NMR studies provide some insight into the elementary steps responsible for the degradation of the surface oxide layer on titanium by the chlorosilane. The effect of Lewis acid additives on the course of the coupling processes is discussed.