Carbohydrate‐Based Pyridine‐2‐carboxamides for Mo‐Catalyzed Asymmetric Allylic Alkylations

Bis(pyridine‐2‐carboxamides) were prepared from 1,2‐diamines obtained from α‐ D ‐glucose and α‐ D ‐mannose. The ligands were assessed in molybdenum‐catalyzed asymmetric allylic alkylations (AAA) by using both methyl ( E )‐3‐phenyl‐2‐propenyl and methyl rac ‐1‐phenyl‐2‐propenyl carbonates and dimethyl malonate as nucleophile under microwave irradiation. High enantioselectivity (99 % ee ) and high regioselectivity (49:1 in favour of the branched isomer) were observed in reactions of the linear achiral substrate in the presence of 10 mol‐% of a catalyst prepared from a ligand derived from glucose. Somewhat lower enantioselectivity (up to 96 % ee ) was observed in reactions with the branched racemic carbonate by using the same ligand.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)