Hydrogenation of dicarboxylic acids to diols using Ruthenium catalyst

Luca Rosi ,  Piero Frediani ,  Dario Vannucchi 

Dipartimento di Chimica, Università di Firenze (UNIFI), Via della Lastruccia 3, Sesto Fiorentino (Firenze) 50019, Italy

Abstract

 Hydrogenation of dicarboxylic acids to diols using Ruthenium catalyst

Piero Frediani, Luca Rosi, Dario Vannucchi
 
Department of Organic Chemistry - University of Florence, via della Lastruccia, 13 - 50019 Sesto Fiorentino (FI)

RuH4(CO)8(PBu3)4 catalyzes selectively the reduction of disubstituited dicarboxylic acids to esters but is not able to reduce the esters to the corresponding alcohols.

On these bases, recently 1, we have settled  a convenient procedure for the reduction of 1,4-dicarboxylic acid to isotopomeric g-butyrolactones containing 2, 4 or 6 deuterium atoms  using Ru4H4(CO)8(PBu3)4 as homogeneus catalyst under a D2 pressure.

Tetradeuterated gamma-butyrolactone-[3,4,5,5-D4] from maleic or fumaric acids, dideuterated gamma-butyrolactone-[5,5-D2] from succinic acid and hexadeuterated gamma-butyrolactone-[3,3,4,4,5,5-D6] from acetylenedicarboxylic acid.

Now our interest is focused on the syntheses of differently deuterated 1,4-butandiols starting from the appropiate dicarboxylic acids. Aware of the ability of the [Ru(acac)3]/MeC(CH2PPh2)3 system to catalyze, in the homogeneous, the hydrogenation of dimetyl oxalate to ethylenglycol, we have explored to employ such system in the one-pot syntheses of 1,4-butanediol (1,4-BD) from gamma-butyrolactone (GBL) or fumaric acid . The catalyst tested gives up to 49.6 yiled of 1,4-BTD from fumaric acid using methanol as solvent.

Reaction conditions and preliminary results are collected in the table below:

Entry Substrate Solvent T

Time

Reaction

Products  Composition (%)
°C h GBL 1,4-BTD DMS MHS
1 Fumaric acid MeOH 120 16 12.8 0.7 74.1 12.4
2 Fumaric acid MeOH 120 48 7.8 49.6 19.2 23.4
3 Fumaric THF 120 48 69.2 8.3 22.5

0.0

5 GBL MeOH 120 48 11.8 48.8 0.0 39.4
6 GBL THF 120 48 77.7 13.8 0.0 0.0

 Substrate 1.77 mmol, Ligand/Ru 1.37, Ru(acac)3 0.021 mmol, Solvent 12 ml, p(H2) 80 bar, Substrate/Zn 1/0.26. DMS: Dimethyl succinate, MHS: Methyl 4-hydroxysuccinate.

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Presentation: Poster at COST D30 Final Evaluation Meeting, by Luca Rosi
See On-line Journal of COST D30 Final Evaluation Meeting

Submitted: 2007-10-22 14:31
Revised:   2009-06-07 00:48
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