Nitrile synthesis by oxidation, rearrangement, dehydration

T1 - A nitrile oxide based entry to 2,3-dihydropyran-4-ones. Synthesis of a protected version of "compactin lactone" in racemic and optically active forms

T1 - Synthesis, spectroscopy, and applications of small nitrile oxides

N2 - Visible-light photoredox catalysis enables the synthesis ofbiologically relevant isoxazolines and isoxazoles fromhydroxyimino acids. The process shows broad functional groupcompatibility and mechanisitic and computational studies supporta visible-light-mediated generation of nitrile oxides by twosequential oxidative single electron transfer processes.


Cycloaddition of benzynes and nitrile oxides: synthesis …

J., Synthesis of pegylated star microgel with core functionality for click chemistry by nitroxide-mediated radical polymerization.

N2 - Efficient syntheses of some pregnane-fused isoxazolines from 16-dehydropregnenolone acetate with different arylnitrile oxides were carried out by 1,3-dipolar cycloadditions. The intermolecular ring-closures occurred in a highly regio- and stereoselective manner permitting the formation of a single 16α,17α-condensed diastereomer in which the O terminus of the nitrile oxide dipole is attached to C-17 of the sterane core. The conversions were found to be affected significantly by the electronic character of the substituents on the aromatic moiety of the 1,3-dipoles. Deacetylation of the primary products resulted in the corresponding 3β-OH analogs. All of the synthesized compounds were subjected to in vitro pharmacological studies for the determination of their antiproliferative effects on four breast cancer cell lines (MCF7, T47D, MDA-MB-231 and MDA-MB-361).


An epoxide is a cyclic ether with a three-atom ring

Small covalent nitrile oxides are important transient species in organic synthesis and widely used especially for dipolar cycloaddition reactions. Due to their instability, their isolation and characterization are challenging. This review focuses on the generation, spectroscopy, structural properties, and synthetic application of small nitrile oxides, XCNO, where the X substituent group is smaller than five atoms, viz. X= hydrogen, halogen, pseudohalogen, alkyl, vinyl, ethynyl, or nitro.

Click Chemistry Publications - Scripps Research Institute

Efficient syntheses of some pregnane-fused isoxazolines from 16-dehydropregnenolone acetate with different arylnitrile oxides were carried out by 1,3-dipolar cycloadditions. The intermolecular ring-closures occurred in a highly regio- and stereoselective manner permitting the formation of a single 16α,17α-condensed diastereomer in which the O terminus of the nitrile oxide dipole is attached to C-17 of the sterane core. The conversions were found to be affected significantly by the electronic character of the substituents on the aromatic moiety of the 1,3-dipoles. Deacetylation of the primary products resulted in the corresponding 3β-OH analogs. All of the synthesized compounds were subjected to in vitro pharmacological studies for the determination of their antiproliferative effects on four breast cancer cell lines (MCF7, T47D, MDA-MB-231 and MDA-MB-361).

Robust, Efficient, and Orthogonal Synthesis of …

To expand the synthetic utility of the halogenated azoles obtained under ruthenium catalysis, we examined selective transformations of the amide and halide functionalities. Palladium-catalyzed cross coupling reactions were briefly evaluated on both the iodo- and bromotriazoles (38 and 5c, ) and bromoisoxazoles (21 and 25). Several examples involving halogenated triazoles are known,[] and following brief reaction pendant azide handles (49). The reaction was run with 10 mol% condition screening, we were likewise successful in replacing the halogen with ethynyl 51, allyl 52, acrylate 53 and aryl 54 groups. The 5-iodotriazole was more reactive compared to its brominated analog, which required increased reaction temperature and extended reaction time. Similarly, bromoisoxazole 21 was converted to the butyl acrylate 55 and allyl 56 derivatives, albeit in modest yield, using slightly modified published protocols.[, , ]