Chemoenzymatic Synthesis of an Odanacatib Precursor through a Suzuki‐Miyaura Cross‐Coupling and Bioreduction Sequence

A series of 1‐aryl‐2,2,2‐trifluoroethanones has been chemically synthesized to later study their bioreduction using stereocomplementary alcohol dehydrogenases (ADHs). Satisfyingly, (R)‐alcohols were obtained in high conversions and selectivities using the ADH from Ralstonia species and the one from...

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Veröffentlicht in:ChemCatChem 2019-12, Vol.11 (23), p.5800-5807
Hauptverfasser: González‐Martínez, Daniel, Gotor, Vicente, Gotor‐Fernández, Vicente
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Gotor, Vicente
Gotor‐Fernández, Vicente
description A series of 1‐aryl‐2,2,2‐trifluoroethanones has been chemically synthesized to later study their bioreduction using stereocomplementary alcohol dehydrogenases (ADHs). Satisfyingly, (R)‐alcohols were obtained in high conversions and selectivities using the ADH from Ralstonia species and the one from Rhodococcus ruber, while the (S)‐enantiomers were independently produced using the ADH from Lactobacillus brevis and the commercially available evo‐1.1.200. In the search for a stereoselective route towards the Odanacatib, an orally bioavailable and selective inhibitor of Cathepsin K, the development of a sequential methodology combining a palladium‐catalyzed cross coupling between 1‐(4‐bromophenyl)‐2,2,2‐trifluoroethanone and 4‐(methylsulfonyl)phenylboronic acid in aqueous medium with the bioreduction of the resulting 2,2,2‐trifluoro‐1‐(4′‐(methylsulfonyl)‐[1,1′‐biphenyl]‐4‐yl)ethanone has been extensively studied. Finally, the desired (R)‐2,2,2‐trifluoro‐1‐(4′‐(methylsulfonyl)‐[1,1′‐biphenyl]‐4‐yl)ethanol was obtained in enantiomerically pure form and 85 % yield with a 128 g L−1 d−1 productivity following a sequential approach. The perfect partnership: A good compatibility between palladium and alcohol dehydrogenase from Ralstonia species has been found for the successful development of a sequential chemoenzymatic transformation towards the formation of a valuable enantiopure Odanacatib precursor.
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Satisfyingly, (R)‐alcohols were obtained in high conversions and selectivities using the ADH from Ralstonia species and the one from Rhodococcus ruber, while the (S)‐enantiomers were independently produced using the ADH from Lactobacillus brevis and the commercially available evo‐1.1.200. In the search for a stereoselective route towards the Odanacatib, an orally bioavailable and selective inhibitor of Cathepsin K, the development of a sequential methodology combining a palladium‐catalyzed cross coupling between 1‐(4‐bromophenyl)‐2,2,2‐trifluoroethanone and 4‐(methylsulfonyl)phenylboronic acid in aqueous medium with the bioreduction of the resulting 2,2,2‐trifluoro‐1‐(4′‐(methylsulfonyl)‐[1,1′‐biphenyl]‐4‐yl)ethanone has been extensively studied. Finally, the desired (R)‐2,2,2‐trifluoro‐1‐(4′‐(methylsulfonyl)‐[1,1′‐biphenyl]‐4‐yl)ethanol was obtained in enantiomerically pure form and 85 % yield with a 128 g L−1 d−1 productivity following a sequential approach. 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Satisfyingly, (R)‐alcohols were obtained in high conversions and selectivities using the ADH from Ralstonia species and the one from Rhodococcus ruber, while the (S)‐enantiomers were independently produced using the ADH from Lactobacillus brevis and the commercially available evo‐1.1.200. In the search for a stereoselective route towards the Odanacatib, an orally bioavailable and selective inhibitor of Cathepsin K, the development of a sequential methodology combining a palladium‐catalyzed cross coupling between 1‐(4‐bromophenyl)‐2,2,2‐trifluoroethanone and 4‐(methylsulfonyl)phenylboronic acid in aqueous medium with the bioreduction of the resulting 2,2,2‐trifluoro‐1‐(4′‐(methylsulfonyl)‐[1,1′‐biphenyl]‐4‐yl)ethanone has been extensively studied. Finally, the desired (R)‐2,2,2‐trifluoro‐1‐(4′‐(methylsulfonyl)‐[1,1′‐biphenyl]‐4‐yl)ethanol was obtained in enantiomerically pure form and 85 % yield with a 128 g L−1 d−1 productivity following a sequential approach. 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subjects Alcohol dehydrogenase
Alcohols
Aqueous solutions
Aromatic compounds
Asymmetric synthesis
Bioavailability
Bioreduction
Cascade reactions
Cross coupling
Enantiomers
Ethanol
Odanacatib
Organic chemistry
Palladium
Rhodococcus
Series (mathematics)
Stereoselectivity
title Chemoenzymatic Synthesis of an Odanacatib Precursor through a Suzuki‐Miyaura Cross‐Coupling and Bioreduction Sequence
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