Kinetics analysis and automated online screening of aminocarbonylation of aryl halides in flow

Temperature, pressure, gas stoichiometry, and residence time were varied to control the yield and product distribution of the palladium-catalyzed aminocarbonylation of aromatic bromides in both a silicon microreactor and a packed-bed tubular reactor. Automation of the system set points and product sampling enabled facile and repeatable reaction analysis with minimal operator supervision. It was observed that the reaction was divided into two temperature regimes. An automated system was used to screen steady-state conditions for offline analysis by gas chromatography to fit a reaction rate model. Additionally, a transient temperature ramp method utilizing online infrared analysis was used, leading to more rapid determination of the reaction activation energy of the lower temperature regimes. The entire reaction spanning both regimes was modeled in good agreement with the experimental data

Brønsted Acid-Catalyzed Straightforward Synthesis of Benzo[b]carbazoles from 2,3-Unsubstituted Indoles

Described is a general and efficient synthesis of valuable benzo[b]carbazoles by Brønsted acid-catalyzed reactions between simple C-2,C-3-unsubstituted indoles and ortho-[α-(hydroxy)benzyl]benzaldehyde acetals. Highly selective migration processes are involved as key steps in the overall cascade sequence that involves the one-pot formation of two new bonds and a cycle in a regioselective fashion.Ministerio de Economia y Competitividad (MINECO) and FEDER (CTQ2010-15358) for financial suuport. P. G.-G. and M.A.F.-R. thank MINECO for "Juan de la Cierva" and "Ramon y Cajal" contractsThis is the peer reviewed version of the following article: Suárez, A., García-García, P., Fernández-Rodríguez, M. A. and Sanz, R. (2014), Brønsted Acid-Catalyzed Straightforward Synthesis of Benzo[b]carbazoles from 2,3-Unsubstituted Indoles. Adv. Synth. Catal., 356: 374–382. doi: 10.1002/adsc.201300868, which has been published in final form at 10.1002/adsc.201300868. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving

Use of triazole-ring formation to attach a Ru/TsDPEN complex for asymmetric transfer hydrogenation to a soluble polymer

The cycloaddition of a chiral ligand containing a terminal alkyne to a soluble polymer containing an azide provides a convenient means for the attachment of an asymmetric transfer hydrogenation catalyst to a soluble polymer support. Using these ligands in complexes with Ru(II), gave good results in terms of conversion and enantioselectivity (up to 95% ee) in ketone reduction reactions