From Olefins to Alcohols: Efficient and Regioselective Ruthenium‐Catalyzed Domino Hydroformylation/Reduction Sequence

Abstract

Auf der Suche nach Alternativen: Ruthenium‐Imidazoylphosphan‐Komplexe katalysieren eine Dominoreaktion aus Hydroformylierung und Reduktion, die Alkene mit guten Selektivitäten und Ausbeuten in Alkohole überführt (siehe Schema). Lineare aliphatische Alkohole wurden unter Reaktionsbedingungen erzeugt, die für industrielle Hydroformylierungen typisch sind.

In Situ FTIR and NMR Spectroscopic Investigations on Ruthenium‐Based Catalysts for Alkene Hydroformylation

“…Imidazolyl monophosphines were obtained from Beller et al at LIKATa nd stored under argon. [18][19][20][21][22] The internal IR standard diphenyl carbonate (99 %, Aldrich) and triphenylphosphine (99 %, Aldrich) were used as received. The following gases were used in this study:s ynthesis gas (CO/H 2 1/1, from 99.997 % carbon monoxide and 99.999 %h ydrogen, Linde), carbon monoxide (99.997 %, Linde), hydrogen (99.9993 %, Linde), and argon (99.999 %, Linde).…”

“…Imidazole-substituted monophosphines selected for this study. [18,20] Figure 6s hows the X-ray molecular structure. Surprisingly,adinuclear complex was obtained.…”

“…[15][16][17] Recently,ab reakthrough was reported by Beller and coworkers, who discovered that ruthenium(0) complexes formed from [Ru 3 (CO) 12 ]a nd modified with imidazole-substituted monophosphines are unusually active towards the formation of the desired aldehyde products. [18][19][20][21][22] Noteworthily,t he new catalysts ystem operates under mild reactionc onditions and allows the conversion of ab road scope of substrates. Moreover,t hese complexes have been successfully applied in cascade reactions such as hydroformylation/reduction [18,21] and hydroaminomethylation.…”

“…[18][19][20][21][22] Noteworthily,t he new catalysts ystem operates under mild reactionc onditions and allows the conversion of ab road scope of substrates. Moreover,t hese complexes have been successfully applied in cascade reactions such as hydroformylation/reduction [18,21] and hydroaminomethylation. [19,22] Withrespect to the optimal reaction conditions it was found that the best catalytic performance was obtained by runningt he reactions in polar organic solvents such as propylenec arbonate.…”

“…The aim of this work was to rationalize the outstanding catalytic performance of the highly versatile system [18][19][20][21][22] reported by Beller et al by application of in situ IR and NMR spectroscopy.O ur special concern was to characterizer esting states spectroscopically under hydroformylation conditions. [20] The interpretation of IR spectra is supported by vibrational analysis through DFT calculations.…”