Enzyme- and Ruthenium-Catalyzed Dynamic Kinetic Asymmetric Transformation of 1,5-Diols. Application to the Synthesis of (+)-Solenopsin A

Abstract

Dynamic kinetic asymmetric transformation (DYKAT) of 1,5-diols via combined lipase and ruthenium catalysis provides enantiomerically pure diacetates in high diastereoselectivity, which can serve as intermediates in natural product synthesis. This is demonstrated by the synthesis of (+)-Solenopsin A.

Dynamic Kinetic Resolution via Hydrolase‐Metal Combo Catalysis in Stereoselective Synthesis of Bioactive Compounds

“…A similar procedure has been reported for the preparation of enantiopure anti‐angiogenic (+)‐solenopsin A (Scheme , b) 12e…”

Tandem Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis

“…Monomeric ruthenium pentamethylcyclopentadiene complex 1 developed by Bäckvall and co-workers [17] has been widely used in tandem with different enzymes to deracemize a wide range of functionalized secondary alcohols, including aliphatic alcohols [18,19], allylic alcohols [20][21][22], chlorohydins [23], diols [24,25], homoallylic alcohols [26], and N-heterocyclic 1,2-aminos alcohols [27] with excellent yields and enantiomeric excess (ee). Recently, complex 1 has been employed to synthesize biologically active 5,6-dihydropyran-2-ones and the corresponding δ-lactones [26].…”

Lipases: Valuable catalysts for dynamic kinetic resolutions

“…Kim et al, 2013;S. Kim et al, 2013;Ko et al, 2007;Koh et al, 1999;Krumlinde et al, 2009;Larsson et al, 1997;Lee et al, 2000;Leijondahl et al, 2009;Lihammar et al, 2011;Mangas-Sánchez et al, 2009;Martín-Matute et al, 2004, 2006Mavrynsky et al, 2009Mavrynsky et al, , 2013Merabet-Khelassi et al, 2011;Norinder et al, 2007;Päiviö et al, 2011;Riermeier et al, 2005;Träff et al, 2008Träff et al, , 2011Warner et al, 2012). These catalysts are homogeneous under the conditions employed in DKR reactions and present differences regarding scope, mode of activation, requirement of additives, compatibility with acyl donors, stability, efficiency and cost.…”

“…This catalyst is activated by bases such as t-BuOK and is able to quickly racemize alcohols under mild temperatures in the presence of lipases, so that it has been employed in the DKR of several alcohols Bogár et al, 2007aBogár et al, , 2007bCsjernyik et al, 2004;Edin et al, 2006;Ema et al, 2012;Engstrom et al, 2011;Fransson et al, 2006;Johnston et al, 2010;S. Kim et al, 2013;Krumlinde et al, 2009;Leijondahl et al, 2009;Lihammar et al, 2011Lihammar et al, , 2013Mangas-Sánchez et al, 2009;Martín-Matute et al, 2004, 2006Norinder et al, 2007;Shuklov et al, 2014;Solarte et al, 2014;Träff et al, 2008Träff et al, , 2011Warner et al, 2012), including the large-scale DKR of 1-phenylethanol to give (R)-1-phenylethanol (Bogár et al, 2007a). The recently reported catalyst 12 is the first cationic ruthenium catalyst to be applied in a chemoenzymatic DKR.…”