5876-79-9Relevant articles and documents
Preparation of fluorohalomethylmagnesium halides using highly active magnesium metal and their reactions
Kví?ala, Jaroslav,?tambasky, Jan,Skalicky, Martin,Paleta, Old?ich
, p. 1390 - 1395 (2007/10/03)
Highly active magnesium (Rieke magnesium) reacts with fluorohalomethanes at -100°C forming the corresponding fluorohalomethylmagnesium halides, which undergo nucleophilic substitution with silyl halides or nucleophilic addition with aldehydes or ketones. Whereas the stability of dibromofluoromethylmagnesium bromide (2a) was sufficient to provide acceptable product yields with dimethylphenylsilyl chloride, benzaldehyde, butyraldehyde or acetophenone as electrophiles, other fluoroorganomagnesium halides, bromodifluoromethylmagnesium bromide (2b), bromochlorofluoromethylmagnesium bromide (2c) and trifluoromethylmagnesium iodide (2d) displayed only very limited stability and thus the corresponding yields of reactions with electrophiles were low.
Efficient diastereoselective pinacol reaction of aliphatic and aromatic aldehydes by combined use of newly utilized titanium(II) bromide and copper
Mukaiyama, Teruaki,Kagayama, Akifumi,Igarashi, Koji
, p. 336 - 337 (2007/10/03)
Newly utilized low-valent titanium reductant, titanium(II) bromide, was conveniently prepared by treating titanium(IV) bromide with hexamethyldisilane. The pinacol reaction of aromatic and aliphatic aldehydes including primary aldehydes proceeded smoothly in dichloromethane-pivalonitrile at temperatures ranging from -23 to 0 °C by the combined use of soluble titanium(II) bromide and copper to give 1,2-diols in good to high yields with good to high dl-selectivities.
Carbonyl coupling reactions catalytic in titanium and the use of commercial titanium powder for organic synthesis
Fürstner, Alois,Hupperts, Achim
, p. 4468 - 4475 (2007/10/02)
The high thermodynamic stability of titanium oxides formed as the inorganic byproducts in McMurry-type 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 β-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.
