Dynamic Asymmetric Hemithioacetal Transformation by Lipase‐Catalyzed γ‐Lactonization: In Situ Tandem Formation of 1,3‐Oxathiolan‐5‐one Derivatives

Abstract

Dynamic hemithioacetal systems were efficiently generated in organic solvents and subsequently allowed to react with a range of lipases. This resulted in direct, dynamic asymmetric transformation of the systems, leading to optically active 1,3-oxathiolan-5-one products. The tandem process identified lipase-catalyzed lactonization as a useful method for the resolution of optimal constituents with high chemo- and stereoselectivities.

Lipases: Valuable catalysts for dynamic kinetic resolutions

“…Similarly, esters of optically pure hemithioacetals may be obtained by lipase-catalyzed transesterification of the respective hemithioacetal formed by reversible reaction from aldehydes and thiols (Brand et al, 1995;Hu et al, 2014;Sakulsombat et al, 2012a;Sanfilippo et al, 2005;Zhang et al, 2014a). This approach has proven to be useful for the preparation of optically pure 1,3-oxathiolan-5-ones, structural motifs that are featured in antiretroviral drugs (Fig.…”

IUPAC 2013 Distinguished Women in Chemistry or Chemical Engineering / New Members of the Royal Swedish Academy of Sciences

“…Ramström’s research is centered on molecular recognition, in particular receptor–ligand interactions and complex chemical networks, and includes topics such as dynamic chemistry, synthesis and catalysis, nanomaterials, and sensors and interfaces. He has reported in Angewandte Chemie on the racemase‐type activity of B. cepacia lipase,7a and in Chemistry—A European Journal on lipase‐catalyzed γ‐lactonization 7b…”

Lipase-catalyzed asymmetric synthesis of oxathiazinanones through dynamic covalent kinetic resolution

“…18,[21][22][23][24]27,28 It was shown that similar enantiomeric excesses (ees) could be obtained with both solvents; however, in toluene, higher conversions and reaction rates were observed. Among the enzymes tested, viz.…”