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Reduction of carboxyl compounds to aldehydes

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Rosenmund Reduction


Fukuyama Reduction


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A highly efficient in situ generation of the Schwartz reagent provides a convenient method for the reduction of amides to aldehydes and the regioselective hydrozirconation-iodination of alkynes and alkenes. These single-step processes proceed in very short reaction time, show excellent functional group compatibility, and use inexpensive and long-storage stable reducing reagents.
Y. Zhao, V. Snieckus, Org. Lett., 2014, 16, 390-393.


A chemoselective activation of a secondary amide with triflic anhydride in the presence of 2-fluoropyridine enables a mild reduction using triethylsilane, a cheap and rather inert reagent. Imines can be isolated after a basic workup or readily transformed to the aldehydes following an acidic workup. The amine moiety can be accessed by addition of Hantzsch ester to the reaction mixture.
G. Pelletier, W. S. Bechara, A. B. Charette, J. Am. Chem. Soc., 2010, 132, 12817-12819.


In a sequential one-pot process for the conversion of sterically demanding N,N-diisopropylamides to aldehydes, amides are activated with EtOTf to form imidates, which are reduced with LiAlH(OR)3 [R = t-Bu, Et] to give aldehydes by hydrolysis of the resulting hemiaminals. The non-nucleophilic base 2,6-DTBMP remarkably improves reaction efficiency. The reaction tolerates various reducible functional groups, including aldehyde and ketone.
P. Xiao, Z. Tang, K. Wang, H. Chen, Q. Guo, Y. Chu, L. Gao, Z. Song, J. Org. Chem., 2018, 83, 1687-1700.


A palladium-catalyzed reduction of 2-pyridinyl esters using hydrosilanes is applicable to the preparation of aliphatic, aromatic, and α,β-unsaturated aldehydes. Various functional groups, such as fluoro, methoxy, aldehyde, acetal, and ester, are tolerated.
J. Nakanishi, H. Tatamidani, Y. Fukumoto, N. Chatani, Synlett, 2006, 869-872.


The combination of Pd(OAc)2/Et3SiH enables ligand-controlled non-decarbonylative and decarbonylative conversions of acyl fluorides. When tricyclohexylphosphine (PCy2) was used as the ligand, aldehydes were obtained as simple reductive conversion products, whereas 1,2-bis(dicyclohexylphosphino)ethane (Cy2P(CH2)2PCy2, DCPE) as the ligand favored the formation of hydrocarbons as decarbonylative reduction products.
Y. Ogiwara, Y. Sakuria, H. Hattori, N. Sakai, Org. Lett., 2018, 20, 4164-4167.


Re2(CO)10 efficiently catalyzes the direct reduction of various carboxylic acids under UV irradiation at ambient temperature. While aliphatic carboxylic acids were readily converted to the corresponding disilylacetals with low catalyst loading in the presence of Et3SiH, aromatic analogues required more drastic conditions.
D. Wei, R. Buhaibeh, Y. Canac, J.-B. Sortais, Org. Lett., 2019, 21, 7713-7716.


Treatment of ethanethiol esters with triethylsilane and palladium on carbon at ambient temperature furnished aldehydes. In addition, a variety of ketones has been prepared by a palladium-catalyzed reaction of ethanethiol esters with organozinc reagents. Both transformations tolerate various functional groups, including esters, ketones, aromatic halides and aldehydes.
H. Tokuyama, S. Yokoshima, T. Yamashita, S.-C. Lin, L. Li, T. Fukuyama, J. Braz. Chem. Soc., 1998, 9, 381-387.


Reduction of ethanethiol esters of α-amino acids to α-amino aldehydes by triethylsilane and catalytic palladium-on-carbon is described. α-Amino aldehydes with Boc, Cbz, or Fmoc protection could be obtained without racemization in high yield.
H. Tokuyama, S. Yokoshima, S.-C. Lin, L. Li, T. Fukuyama, Synthesis, 2002, 1121-1123.


A copper hydride-catalyzed enantioselective reduction of α,β-unsaturated carboxylic acids provides various saturated β-chiral aldehydes in good yields, with high levels of enantioselectivity and broad functional group tolerance. A reaction pathway involving a ketene intermediate is proposed.
Y. Zhou, J. S. Bandar, R. Y. Liu, S. L. Buchwald, J. Am. Chem. Soc., 2018, 140, 606-609.


A copper hydride-catalyzed enantioselective reduction of α,β-unsaturated carboxylic acids provides various saturated β-chiral aldehydes in good yields, with high levels of enantioselectivity and broad functional group tolerance. A reaction pathway involving a ketene intermediate is proposed.
Y. Zhou, J. S. Bandar, R. Y. Liu, S. L. Buchwald, J. Am. Chem. Soc., 2018, 140, 606-609.