Extended Data Fig. 8: Orbital analysis for the a) LUMOs of the dienophile, b) HOMO of the diene, c) the LUMO of the dienophile bound to R443 (MaDA) and d) the dienophile bound to R294(MaDA-3).
From: Enzymatic control of endo- and exo-stereoselective Diels–Alder reactions with broad substrate scope
Orbital energies are calculated using ωB97X-D/6-31G(d,p) CPCM (diethyl ether) level of theory. All orbital energies are reported in eV. The reaction proceeds via a normal-electron demand DA reaction, with HOMODiene-LUMOdienophile gap shrinking from 6.7 eV for the uncatalyzed reaction between a and b to 5.9 eV between b and c by 0.8 eV for R443-Dienophile (MaDA). The HOMODiene-LUMOdienophile gap shrunk to 6.0 eV between b and d by 0.7 eV for R294-Dienophile (MaDA-3).
