Dynamic kinetic resolution in asymmetric synthesis information
Chemistry
Dynamic kinetic resolution in chemistry is a type of kinetic resolution where 100% of a racemic compound can be converted into an enantiopure compound. It is applied in asymmetric synthesis. Asymmetric synthesis has become a much explored field due to the challenge of creating a compound with a single 3D structure.[1] Even more challenging is the ability to take a racemic mixture and have only one chiral product left after a reaction. One method that has become an exceedingly useful tool is dynamic kinetic resolution (DKR).[2][3] DKR utilizes a center of a particular molecule that can be easily epimerized so that the (R) and (S) enantiomers can interconvert throughout the reaction process. At this point the catalyst can selectively lower the transition state energy of a single enantiomer, leading to almost 100% yield of one reaction pathway over the other. The figure below is an example of an energy diagram for a compound with an (R) and (S) isomer.[4]
Energy diagram of an (R) and (S) isomer. With addition of a catalyst, one transition state (TS) is lower and thus becomes the kinetically favored pathway.
If a catalyst is able to increase ΔΔG‡ to a sufficient degree, then one pathway will dominate over the other, leading to a single chiral product. Manipulating kinetics therefore becomes a powerful way to achieve asymmetric products from racemic starting materials. There have been numerous uses of DKR in the literature that have provided new methods in pharmaceuticals[5] as well as routes to natural products.[6]
^El, G. M. T.; Williams, J. M. J. Curr. Opin. Chem. Biol.1999, 3, 11–15.
^Pellissier, H. Tetrahedron2008, 64, 1563–1601.
^Coldham, I.; Dufour, S.; Haxell, T. F. N.; Patel, J. J.; Sanchez-Jimenez, G. J. Am. Chem. Soc.2006, 128, 10943–10951.
^Hanefeld, U.; Veum, L. Tetrahedron: Asymmetry, 2004, 15, 3707–3709.
^Blacker, J.; Headley, C. E. In Green Chemistry in the Pharmaceutical Industry; 2010; pp. 269–288.
^Goodyear, M. D.; Hill, M. L.; West, J. P.; Whitehead, A. J. Tetrahedron Lett.2005, 46, 8535–8538.
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