Toward coherent anti‐Stokes Raman scattering‐Raman optical activity for reaction monitoring in organocatalysis: Chiral vibrational signatures of the two atropisomers (R)‐ and (S)‐MOM‐BINOL in solution

Abstract

AbstractCoherent anti‐Stokes Raman scattering‐Raman optical activity (CARS‐ROA) is a coherent version of spontaneous ROA spectroscopy, the latter being a well‐established chirally sensitive vibrational spectroscopic technique. A central major advantage of heterodyne‐detected CARS‐ROA over ROA is the drastic reduction of acquisition times from several hours to approximately 1 min due to the high ratio of the chiral Raman signal relative to the achiral CARS background. Here, we present the first demonstration of heterodyne‐detected CARS‐ROA of chiral molecules dissolved in an achiral solvent by using an experimental setup built from a conventional broadband CARS spectrometer. Specifically, the two atropisomers (R/S) of 2,2′‐Bis(methoxymethoxy)‐1,1′‐binaphthyl, a methoxymethyl (MOM) bis‐protected derivative of 1,1′‐Bi‐2‐naphthol (BINOL), dissolved in the achiral organic solvent dichloromethane (DCM) were characterized by employing ~1 ps, 1 mW of pump pulses and ~60 fs, 10 mW of Stokes pulses within approximately 4‐min acquisition time. MOM‐BINOL is an important precursor for the synthesis of a great variety of many chiral auxiliaries including binaphthyl phosphoric acids, which are an important class of chiral organocatalysts used in asymmetric reactions. Overall, this work is a first step toward kinetic reaction monitoring in organocatalysis by coherent ROA providing the necessary short acquisition times.