In Situ Generated Gold Nanoparticles on Active Carbon as Reusable Highly Efficient Catalysts for a C sp 3 -C sp 3 Stille Coupling.

Gold nanoparticle catalysts are important in many industrial production processes. Nevertheless, for traditional C sp 2 -C sp 2 cross-coupling reactions they have been rarely used and Pd catalysts usually give a superior performance. Herein we report that in situ formed gold metal nanoparticles are highly active catalysts for the cross coupling of allylstannanes and activated alkylbromides to form C sp 3 -C sp 3 bonds. Turnover numbers up to 29 000 could be achieved in the presence of active carbon as solid support, which allowed for convenient catalyst recovery and reuse. The present study is a rare case where a gold metal catalyst is superior to Pd catalysts in a cross-coupling reaction of an organic halide and an organometallic reagent.

Intervalence of two planar chiral 2-methylferrocenyl groups over a diaurum bridge.

The electronic structure of recently reported diaurum (AuIAuI and XAuII-AuIIX) complexes, containing two methylferrocenyloxazoline ligands are described. Oxidations occurred at the methylferrocenyl and the monocation complex containing AuIAuI bridge was valence localized while the AuII-AuII complex was valence delocalized, i.e., Fe2.5+/Fe2.5+. These findings were supported by electrochemical, and spectroscopic measurements and further supported by computational analysis (DFT).

Diastereoselective synthesis, structure and reactivity studies of ferrocenyloxazoline gold(i) and gold(ii) complexes.

In the last few decades, gold complexes have demonstrated huge potential for soft Lewis acid catalysis. Despite the intensive research on Au complexes and planar chiral metallacycles, enantiopure ferrocenylgold complexes have - surprisingly - not been reported until the studies presented in this article. Herein, we report the asymmetric synthesis of planar chiral ferrocenyl Au(i) complexes. These dinuclear species form helically chiral ten-membered (NCCCAu)2 rings stabilized by aurophilic interactions. In supramolecular solid state structures, linear, zigzag or helical Au(i) wires with regular AuAu separations were observed. The dissolved dinuclear entities could be oxidized by Au(i) to unique ferrocenyl Au(ii) complexes featuring short Au(ii)-Au(ii) bonds, while the ferrocene core remained intact. However, our initial studies revealed the issue of configurational lability of the ferrocenyl Au(ii) complexes in terms of the element of planar chirality in the presence of the gold source, (Me2S)AuCl. This was successfully addressed by a systematic study implementing permanent σ-donor ortho-protecting groups such as methyl and trimethylsilyl, which impede an epimerization event. Oxidation of the dinuclear Au(i) complexes was also accomplished by oxidative addition reactions with halogenated solvents, preferably CHCl3. Additional reactivity studies revealed that dinuclear Au(ii) dihalide complexes are also formed with reactive alkylhalides such as iodomethane, benzylbromide and benzyliodide. Interestingly, the whole spectral range of colors (violet, blue, green, yellow, and red) is covered by the title complexes depending on the Au oxidation state and the anionic ligands in the Au(ii) complexes. This appears to be quite unusual for ferrocenes, which typically adopt orange to red colors in a non-oxidized state.

Synthesis of the AB ring system of clifednamide utilizing Claisen rearrangement and Diels-Alder reaction as key steps.

In order to construct the functionalized AB ring system of clifednamide, member of the class of macrocyclic tetramic acid lactams, a synthesis was developed which utilized an Ireland-Claisen rearrangement and an intramolecular Diels-Alder reaction. Starting from di-O-isopropylidene-d-mannitol the allyl carboxylate precursor for the sigmatropic rearrangement was prepared. This rearrangement proceeded diastereoselectively only in the presence of an allyl silyl ether instead of the parent enone in the side chain, as suggested by deuteration experiments. A subsequent Diels-Alder reaction yielded the target ethyl hexahydro-1H-indene-carboxylate with high diastereoselectivity. Quantum-chemical investigations of this intramolecular Diels-Alder reaction support the proposed configuration of the final product.