Enantioselective N-heterocyclic carbene-catalyzed nucleophilic dearomatization of alkyl pyridiniums† †Electronic supplementary information (ESI) available: Experimental conditions and compound characterization. CCDC 1555492. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc02648j Click here for additional data file. Click here for additional data file.

All reactions were carried out with magnetic stirring under an atmosphere of argon in oven-dried glassware. Methanol was purchased from Sigma-Aldrich and stored in an anhydrous atmosphere. Sodium acetate was purchased from Aldrich and stored under anhydrous atmosphere. H NMR spectra were recorded on Varian 400 MHz spectrometer at ambient temperature or a Bruker Avance III 500 (500 MHz). Data is reported as follows: chemical shift in parts per million (δ, ppm) from CDCl3 (7.26 ppm) or acetone-D6 (2.03 ppm), multiplicity (s = singlet, bs = broad singlet, d = doublet, t = triplet, q = quartet, and m = multiplet), coupling constants (Hz). CNMR were recorded on Varian 400 MHz (at 100 MHz) spectrometer or a Bruker Avance III 500 (125 MHz) at ambient temperature. Chemical shifts are reported in ppm from CDCl3 (77.36 ppm) or acetoneD-6 (205.87, 30.6 ppm). Mass spectra were recorded on an Agilent 6130 Quadrupole LC/MS. HPLC spectra were obtained on an Agilent 1100 series system. Optical rotations were obtained on an Autopol III automatic polarimeter or a Jasco DIP 1000 digital polarimeter. Infrared spectra were recorded on a Perkin Elmer Spectrum Two (Diamond ATR) IR or a Nicolet iS-50 FT-IR spectrometer. Thin layer chromatography was performed on SiliCycle® 250μm 60A plates. Visualization was accomplished with UV light or KMnO4 stain followed by heating.