A biocatalytic method for the chemoselective aerobic oxidation of aldehydes to carboxylic acids

Abstract

Aldehyde dehydrogenases enable the chemospecific oxidation of structurally diverse aldehydes to carboxylic acids in aqueous environment and using only air.

Broadening the Scope of Biocatalysis in Sustainable Organic Synthesis

“…[104] NAD-dependent aldehyde dehydrogenase (ALDH) catalyzes the aerobic oxidation of aldehydes to the corresponding carboxylic acids and three recombinant ALDHs have been used, in combination with NOx for cofactor recycling, for the aerobic oxidation of awide variety of aldehydes with high chemoselectivities. [105] Interestingly,a nA LDH was combined with an enereductase (ERED) in ah ydrogen-borrowing strategy for the conversion of a,b-unsaturated aldehydes into the corresponding a-substituted carboxylica cids with highc hemo-and stereoselectivities (Scheme 10). [106]…”

The Hitchhiker's guide to biocatalysis: recent advances in the use of enzymes in organic synthesis

“…146,147 NAD-dependent aldehyde dehydrogenase (ALDH) catalyses the aerobic oxidation of aldehydes to the corresponding carboxylic acids and three recombinant ALDHs have been used, in combination with NOx for cofactor recycle, for the highly selective aerobic oxidation of a wide variety of aldehydes. 148 Combination of an ALDH with an ene-reductase (ERED) afforded a hydrogen-borrowing strategy for the conversion of a,bunsaturated aldehydes to the corresponding a-substituted carboxylic acids in high chemo-and stereoselectivities (Scheme 13). 149 Baeyer-Villiger Monooxygenases (BVMOs) are synthetically interesting avin-dependent enzymes that catalyse the aerobic oxidation of ketones and cyclic ketones to esters, 150,151 and lactones, respectively.…”

Mechanistic investigations on Pinnick oxidation: a density functional theory study

“…The oxidation of aldehydes to carboxylic acids is a fundamental transformation in organic chemistry that is applied in many syntheses (examples of the use of Pinnick oxidation in synthesis of some bioactive molecules [1][2][3][4][5], Pinnick-type protocol for amidation of aldehyde [6]). Despite the variety of reagents available to achieve this oxidation (for general transformation of aldehyde into carboxylic acid, see [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21]), few of them are suitable for a broad range of aldehydes and/or tolerate a wide range of functional groups [22,23]. Beside selectivity problems, high costs and complexity of the reaction conditions made the application of this transformation on a large scale reasonably difficult.…”

“…Energy profile for oxidation of acrylaldehyde(7) to acrylic acid (11); In the absence (a) and presence (b) of explicit t-BuOH. NMR spectra were recorded in CDCl 3 ( purchased from Cambridge Isotope Laboratories, Inc.) at 298 K using Bruker AVII400 (400 MHz) spectrometer.…”

“…NMR of (a) t-BuOH, (b) acrolein(7) and (c) 1 : 4 mixture of 7:t-BuOH. Red star indicates the position of the very weak deshielded OH signal of interest.18.…”