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Mn2(CO)10 (10 mol%), Et3SiH (10 equiv.), for 24 h under UV irradiation. The
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product was isolated as the 2,4-dinitrophenylhydrozone adduct after hydrolysis.
DOI: 10.1039/C3CC45349A
65
M. Marlett and W. S. Park, J. Org. Chem., 1990, 55, 296; (h) F. Sato,
It is noteworthy that heteroaromatic carboxylic acids such 1p
and 1q bearing respectively a thiophenyl and an indolyl
moieties are reduced in good yields (70% and 88%,
respectively, entries 16 and 17). On the other hand, aliphatic
carboxylic acids, such as palmitic (1r) and tetradecanoic (1s)
acids gave after hydrolysis the corresponding aldehydes in
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5
10 very good yields (92 and 81%, entries 18 and 19). The
presence of internal, non conjugated C=C double bond is
tolerated, as shown by the sole reduction of the carboxylic
group in the oleic acid 1t (entry 20), whereas in the case of a
terminal C=C double bond like in the hept-6-enoic acid 1u, a
15 mixture resulting from the partial hydrosilylation of the
alkene moieties was obtained (60% of the insaturated
disilylacetal and 32% of the trisilylated product resulting from
the hydrosilylation of both the acid and the alkene groups
(entry 21). Interestingly, the diacid 1v leads to the formation
20 of the protected dialdehyde in excellent yield (97%, entry 22).
Finally, acetic acid and formic acid were also nicely converted
to the corresponding aldehydes, which were isolated as their
hydrazone derivatives in good yields (81 % and 52%, entries
23 and 24). In contrast, trifluoroacetic acid was not reduced
25 under similar condition (entry 25).
75
B. W. Day, Tetrahedron Lett., 2006, 47, 6289; (f) D. V. Gutsulyak
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The reactivity of benzoic carboxylic acid derivatives was also
investigated under similar conditions: the reduction of benzoic
acid, p-methyl and p-methoxybenzoic acids leads to the
exclusive formation of the corresponding aldehydes in modest
30 yields, respectively 39%, 29% and 35% yields after hydrolysis
(See Electronic Supporting Information).
In summary, we have developed the first reduction of
carboxylic acids to aldehydes catalysed by commercially
available and inexpensive manganese carbonyl complex
35 Mn2(CO)10 in the presence of triethylsilane as an affordable
and stable reducing agent. The reaction proceeds at room
temperature under UV irradiation. Of notable interest is the
isolation of the stable protected aldehydes as their
disilylacetals, which can be hydrolysed to the corresponding
40 aldehydes.
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Notes and references
a UMR 6226 CNRS-Université Rennes 1, Institut des Sciences Chimiques
de Rennes, Team Organometallics: Materials and Catalysis, Centre for
Catalysis and Green Chemistry Campus de Beaulieu, 263 av. du Général
45 Leclerc, 35042 Rennes Cedex, France Fax: (+) 33 2 23 23 69 39 E-mail:
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Dr. S. Chevance UMR 6226 CNRS-Université Rennes 1, Institut des
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Sciences Chimiques de Rennes Team Ingénierie chimique et molécules
pour le vivant Campus de Beaulieu, 263 av. du Général Leclerc, 35042
50 Rennes Cedex, France
† Electronic Supplementary Information (ESI) available. See
DOI: 10.1039/b000000x/
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