93367-12-5Relevant academic research and scientific papers
A One-Pot Two-Step Enzymatic Pathway for the Synthesis of Enantiomerically Enriched Vicinal Diols
Giovannini, Pier Paolo,Müller, Michel,Presini, Francesco,Baraldi, Serena,Ragno, Daniele,Di Carmine, Graziano,Jacoby, Christian,Bernacchia, Giovanni,Bortolini, Olga
, p. 973 - 978 (2021/02/01)
Enantiomerically enriched 1,2-diols are prominent compounds that find numerous applications in organic chemistry. They are privileged building blocks for the synthesis of APIs (Active Pharmaceutical Ingredients), broadly used as chiral ligands in asymmetric catalysis, and efficient auxiliaries employed to control the stereochemical outcome of total synthesis. Among the number of strategies developed for the preparation of these molecules, enzyme mediated reactions have gained a crucial role in the toolbox of organic chemists for their high efficiency and sustainability. Herein we describe a one-pot two-step protocol designed by combining a thiamine diphosphate (ThDP)-dependent lyase and a NADH-dependent reductase. The ThDP-dependent acetoin:dichlorophenolindophenol oxidoreductase (Ao : DCPIP OR) is exploited to produce enantioenriched α-hydroxyketones through the benzoin-type condensation of methylacetoin with either aldehydes or activated ketones. The enantioenriched α-hydroxyketones undergo the selective reduction into the corresponding 1,2-diols in the same reaction mixture due to the addition of NAD+ and of the NADH-dependent acetylacetoin reductase (AAR). Sodium formate was selected as the sacrificial reductive reactant to generate and recycle in situ the precious NADH by formate-dehydrogenase. Unprecedented reported details on the cloning and expression of the AAR are reported as well.
Selective Transformation of 2,3-Epoxy Alcohols and Related Derivatives. Strategies for Nucleophilic Attack at Carbon-1
Behrens, Carl H.,Ko, Soo Y.,Sharpless, K. Barry,Walker, Frederick J.
, p. 5687 - 5696 (2007/10/02)
In connection with the continuing recent interest in the stereoselective synthesis of epoxy alcohols, a systematic investigation of the bimolecular nucleophilic ring-opening reactions of acyclic 2,3-epoxy alcohols was undertaken.Strategies for nucleophilic attack at C-1 of a 2,3-epoxy alcohol, each of which depends upon the regioselective ring-opening of a 1,2-epoxy 3-ol, were explored.Under Payne rearrangement conditions, t-BuSNa was found to react with 2,3-epoxy alcohols to afford 1-tert-butylthio 2,3-diols.These diols can be readily converted to 1,2-epoxy 3-ols via S-alkylation followed by treatment with base.Alternatively, 1,2-epoxy 3-ols can be prepared from 2,3-epoxy alcohols by sulfonylation and acidic hydrolysis followed by ring-closure of the diol sulfonate intermediate.Dialkylamines were also found to react selectively with 2,3-epoxy alcohols under Payne rearrangement conditions to afford 1-amino 2,3-diols.
