Efficient Asymmetric Simmons-Smith Cyclopropanation and Diethylzinc Addition to Aldehydes Promoted by Enantiomeric Aziridine-Phosphines

Abstract

During an implementation of current research, a set of optically pure chiral aziridines and aziridine imines bearing a phosphine moiety was prepared with high values of chemical yield. The above chiral heteroorganic derivatives were tested for catalytic utility as chiral ligands in asymmetric Simmons-Smith cyclopropanation and asymmetric diethylzinc addition to various aldehydes. Most of the desired products were formed in high chemical yields, with satisfactory values of enantiomeric excess (sometimes more than 90%) and diastereomeric ratios (in case of cyclopropanation reaction).

Recent advances in the accessibility, synthetic utility, and biological applications of aziridines

“…Aziridines were also reported to be useful catalysts. 95 Rachwalski and co-workers described an asymmetric Morita–Baylis–Hillman reaction of methyl vinyl ketone and methyl acrylate ( 339 ) with various aromatic aldehydes ( 340 ) using chiral aziridine-phosphines ( 341 ) as chiral catalysts (Scheme 60). 96…”

A Novel One‐Step Synthesis of Silicon‐Containing Arylacetylene Resin Catalyzed by Et2Zn with Excellent Processability and Thermal Properties

“…Diethylzinc (Et 2 Zn) is a metal organic compound which is widely used for the purpose of organic synthesis. [27][28][29][30] Okura et al developed a coupling reaction for alkynylzinc reagents with aryl and alkenyl iodides and without the aid of transition metal catalysis by mixing and heating all the materials including terminal alkynes and Et 2 Zn (in a 2 : 1 ratio). [31] Huang et al reported the first example of Et 2 Zn mediated silylation of 1-aklynes and chlorosilanes and mechanistic studies that support Zn alkynilides as intermediates in the reaction.…”

Aziridine Ring Opening as Regio- and Stereoselective Access to C-Glycosyl-Aminoethyl Sulfide Derivatives

“…Chiral aziridines are useful intermediates in the synthesis of biologically significant compounds due to their ability to undergo nucleophilic ring opening reactions [ 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 ]. Considering our previous results on carbohydrate chemistry [ 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 ] and based on our experience in synthesis and catalytic activity in the asymmetric synthesis of chiral aziridines [ 59 , 60 , 61 , 62 , 63 , 64 , 65 ], we decided to couple aziridines to glycals with D-gluco and D-galacto configurations via C -glycosidic bonding, with the final formation of C -glycosyl-aminoethyl sulfide derivatives.…”