Chemistry. 2004 Dec 03;10(24):6313-21. doi: 10.1002/chem.200400296.

Oxorhenium complexes as aldehyde-olefination catalysts.

Chemistry (Weinheim an der Bergstrasse, Germany)

Ana M Santos, Filipe M Pedro, Ameya A Yogalekar, Isabel S Lucas, Carlos C Romão, Fritz E Kühn

PMID: 15526317 DOI: 10.1002/chem.200400296

Abstract

Several oxorhenium compounds in the formal oxidation states V and VII are examined as catalysts for the aldehyde-olefination starting from diazo compounds, phosphines, and aldehydes. Of these, [ReMeO2(eta2-alkyne)] complexes provide the simplest catalysts to study, although [ReOCl3(PPh3)2] still remains the most efficient rhenium catalyst for aldehyde-olefination described to date. Prior to the reaction with the Re catalysts the phosphine and the diazo compound react to form a phosphazine. No catalytic reaction occurs in cases where no phosphazine formation is observed. The first step of the catalytic cycle involves the formation of a carbene intermediate by the reaction of phosphazine and catalyst under extrusion of phosphine oxide and dinitrogen. In a second step the carbene reacts with aldehyde under olefin formation and catalyst regeneration. Excess of alkyne as well as the presence of ketones slows down the catalytic reaction. The olefination of 4-nitrobenzaldehyde with diazomalonate is possible with these Re catalysts. In contrast, this reaction does not take place either in the classical Wittig fashion from Ph3P=C(CO2Et)2 and aldehyde or by use of all other catalysts for aldehyde olefination reactions reported to date. Catalytic ylide formation from diazo compounds seems therefore not to be the only pathway through which catalytic aldehyde-olefination reactions can proceed.

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