Iron‐ and Bismuth‐Catalyzed Asymmetric Mukaiyama Aldol Reactions in Aqueous Media

We have developed asymmetric Mukaiyama aldol reactions of silicon enolates with aldehydes catalyzed by chiral Fe^II and Bi^III complexes. Although previous reactions often required relatively harsh conditions, such as strictly anhydrous conditions, very low temperatures (?78 °C), etc., the reactions reported herein proceeded in the presence of water at 0 °C. To find appropriate chiral water‐compatible Lewis acids for the Mukaiyama aldol reaction, many Lewis acids were screened in combination with chiral bipyridine L1 , which had previously been found to be a suitable chiral ligand in aqueous media. Three types of chiral catalysts that consisted of a Fe^II or Bi^III metal salt, a chiral ligand ( L1 ), and an additive have been discovered and a wide variety of substrates (silicon enolates and aldehydes) reacted to afford the desired aldol products in high yields with high diastereo‐ and enantioselectivities through an appropriate selection of one of the three catalytic systems. Mechanistic studies elucidated the coordination environments around the Fe^II and Bi^III centers and the effect of additives on the chiral catalysis. Notably, both Brønsted acids and bases worked as efficient additives in the Fe^II‐catalyzed reactions. The assumed catalytic cycle and transition states indicated important roles of water in these efficient asymmetric Mukaiyama aldol reactions in aqueous media with the broadly applicable and versatile catalytic systems.     

Osmium(III) and Osmium(V) Complexes Bearing a Macrocyclic Ligand: A Simple and Efficient Catalytic System for cis‐Dihydroxylation of Alkenes with Hydrogen Peroxide

A simple protocol that uses [Os^III(OH)(H₂O)(L ‐N₄Me₂)](PF₆)₂ ( 1 ; L ‐N₄Me₂=N,N′‐dimethyl‐2,11‐diaza[3.3](2,6)pyridinophane) as a catalyst and H₂O₂ as a terminal oxidant for efficient cis‐1,2‐dihydroxylation of alkenes is presented. Unfunctionalized (or aliphatic) alkenes and alkenes/styrenes containing electron‐withdrawing groups are selectively oxidized to the corresponding vicinal diols in good to excellent yields (46–99 %). In the catalytic reactions, the stoichiometry of alkene:H₂O₂ is 1:1, and thus the oxidant efficiency is very high. For the dihydroxylation of cyclohexene, the catalytic amount of 1 can be reduced to 0.01 mol % to achieve a very high turnover number of 5500. The active oxidant is identified as the Os^V(O)(OH) species ( 2 ), which is formed via the hydroperoxide adduct, an Os^III(OOH) species. The active oxidant 2 is successfully isolated and crystallographically characterized.     

Doped Nano‐Sized Copper(I) Oxide (Cu2O) on Melamine?Formaldehyde Resin: a Highly Efficient Heterogeneous Nano Catalyst for ‘Click’ Synthesis of Some Novel 1H‐1,2,3‐Triazole Derivatives Having Antibacterial Activity

A facile and simple protocol for the 1,3‐dipolar cycloaddition of organic azides with terminal alkynes catalyzed by doped nano‐sized Cu₂O on melamine? formaldehyde resin (nano‐Cu₂O? MFR) as a new and convenient heterogeneous catalyst is described. In this method, ‘click’ cycloaddition of various structurally diverse β‐azido alcohols and alkynes in the presence of nano‐Cu₂O? MFR in H₂O/THF 1 : 2 furnished the corresponding 1,4‐disubstituted 1H‐1,2,3‐triazole adducts 1a – 1o in good to excellent yields at room temperature (Scheme and Table 3). The nano‐Cu₂O? MFR was characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD), inductively coupled plasma (ICP) analysis, and FT‐IR. The nano‐Cu₂O? MFR could be easily recovered and recycled from the reaction mixture and reused for many consecutive trials without significant decrease in activity (Table 4). The in vitro antibacterial activities of all synthesized compounds were tested on several Gram‐positive and/or Gram‐negative bacteria (Table 5). The results demonstrate the promising antibacterial activity for some of the synthesized compounds.