Recently, DNA has been evaluated as a chiral scaffold for metal complexes to construct so called 'DNA-based hybrid catalysts', a robust and inexpensive alternative to enzymes. The unique chiral structure of DNA allows the hybrid catalysts to catalyze various asymmetric synthesis reactions. However, most current studies used aqueous buffers as solvents for these asymmetric reactions, where subst...

Carbon-carbon bond formation is the basis for the biogenesis of nature's essential molecules. Consequently, it lies at the heart of the chemical sciences. Chiral catalysts have been developed for asymmetric C-C bond formation to yield single enantiomers from several organometallic reagents. Remarkably, for extremely reactive organolithium compounds, which are among the most broadly used reagent...

The discovery and development of conceptually new chiral bifunctional transition metal-based catalysts for asymmetric reactions is described. The chiral bifunctional Ru catalyst was originally developed for asymmetric transfer hydrogenation of ketones and imines and is now successfully applicable to enantioselective C-C bond formation reaction with a wide scope and high practicability. The depr...

Chiral polyborate based Brønsted acids prepared from the VANOL and VAPOL ligands are known to catalyze the reaction of diarylmethyl imines with diazoesters to give cis-aziridines. In the present work, this same catalyst is shown to catalyze the reaction of the same imines with diazoacetamides to give trans-aziridines with the same high asymmetric inductions as seen with cis-aziridines, enabling...

Optically active amines are attracting increasing interest in the food, agrochemical, and pharmaceutical industries as building blocks for novel compounds and as templates for asymmetric synthesis. One of the most common methods for preparing amines is the reductive amination of carbonyl compounds. We have successfully explored the rhodiumcatalyzed asymmetric reductive amination with hydrogen a...

Synthesis of enantiomerically pure isoxazolidine via an asymmetric 1,3- dipolar cycloaddition reaction of nitrone with electron-deficient dipolarophile was described. The process occurs at room temperature in aqueous ethanol as a green solvent and in the presence of a bidendate bis(imine)–Cu(II)triflate complex as catalyst. The reaction mechanism is discussed on the basis of the assignment of t...

A hypothesis concerning asymmetric induction by chiral catalysts is posited, tested, and found to be valid. The hypothesis states that chiral catalysts that are efficient at inducing asymmetry will have their region of maximum stereoinduction spatially congruent with the site of chemistry but inefficient catalysts will not. A simple mapping strategy (stereocartography) is used to assess where t...

Catalytic use of peroxomolybdate for asymmetric transformations has attracted increasing attention due to its catalytic properties and application in catalysis. Herein, we report chiral bisguanidinium dinuclear oxodiperoxomolybdosulfate [BG]2+[(μ-SO4)Mo2O2(μ-O2)2(O2)2]2- ion pair, as a catalyst for enantioselective sulfoxidation using aqueous H2O2 as the terminal oxidant. The ion pair catalyst ...

Although significant progress has been made in the catalytic asymmetric reduction of ketones and olefins over the last few decades, the asymmetric reduction of imines remains a major challenge. Enantioselective reductive amination with organocatalysts has recently been reported, and a number of transition-metal-based catalysts, such as those containing Rh, Ru, Ti, Zr, and Ir, have been applied ...