Bifunctional Catalysts Stabilized on Nanocrystalline Magnesium Oxide for One‐Pot Synthesis of Chiral Diols

New bifunctional catalysts composed of PdCl 4 2− , OsO 4 2− and OsO 4 2− , WO 4 2− designed and prepared by a counterionic stabilization technique involving the reactions of Na 2 PdCl 4 ‐K 2 OsO 4 and K 2 OsO 4 ‐Na 2 WO 4 with nanocrystalline MgO are well characterized. These bifunctional catalysts, NAP‐Mg‐PdOs and NAP‐Mg‐OsW perform tandem Heck asymmetric dihydroxylation and asymmetric dihydroxylation‐ N ‐oxidation reactions, respectively, in the presence of the chiral ligand 1,4‐bis(9 ‐o‐ dihydroquinidinyl)phthalazine [(DHQD) 2 PHAL] in a single pot. It is quite impressive to note that H 2 O 2 is used as a terminal oxidant to provide N ‐methylmorpholine N ‐oxide (NMO) in situ by the oxidation of N ‐methylmorpholine (NMM) in the asymmetric dihydroxylation‐ N ‐oxidation catalyzed by NAP‐Mg‐OsW.