153595-69-8

Upstream product

• 5271-67-0 2-Thiophenecarbonyl chloride 
• 603-35-0 triphenylphosphine 
• 2046-39-1 2-thiophenecarbonyl azide 
• 17698-15-6 N-hydroxythiophene-2-carboxamide 
• 1373758-55-4 3-(thiophen-2-yl)-1,4,2-dioxazole-5-one 
• 1400655-60-8 (thiophen-2-yl)formamido 2,2-dimethylpropanoate 

Downstream Products

• 1003-31-2 thiophene-2-carbonitrile 

Relevant academic research and scientific papers

Interweaving Visible-Light and Iron Catalysis for Nitrene Formation and Transformation with Dioxazolones

Herein, visible-light-driven iron-catalyzed nitrene transfer reactions with dioxazolones for intermolecular C(sp3)-N, N=S, and N=P bond formation are described. These reactions occur with exogenous-ligand-free process and feature satisfactory to excellent yields (up to 99 %), an ample substrate scope (109 examples) under mild reaction conditions. In contrast to intramolecular C?H amidations strategies, an intermolecular regioselective C?H amidation via visible-light-induced nitrene transfer reactions is devised. Mechanistic studies indicate that the reaction proceeds via a radical pathway. Computational studies show that the decarboxylation of dioxazolone depends on the conversion of ground sextet state dioxazolone-bounding iron species to quartet spin state via visible-light irradiation.

Method for synthesizing phosphinimide compound

The invention relates to a method for synthesizing a phosphonimide compound, and belongs to the field of metal catalytic organic synthesis. The method for synthesizing the phosphonimide compound comprises the following steps: adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, carrying out a reaction at a room temperature in an air atmosphere, and after the reaction is completed, carrying out post-treatment so as to obtain the phosphinimide compound. The method for synthesizing the phosphonimide compound disclosed by the invention has the following beneficial effects: (1) the range of a substrate is wide; (2) the catalyst is relatively low in price and less in usage amount; (3) the reaction operation is simple;and (4) the reaction yield is high, and high yield can still be obtained when the reaction is amplified to a gram level.

Unprecedented Transformation of a Directing Group Generated in Situ and Its Application in the One-Pot Synthesis of 2-Alkenyl Benzonitriles

An unprecedented protocol for the transformation of benzoyl azides into benzonitrile derivatives via iminophosphoranes generated in situ is described. The strategy was successfully applied to the de-novo synthesis of 2-alkenylated benzonitrile derivatives from benzoyl azides through ortho CH activation/alkenylation followed by subsequent rearrangement. The salient features of this protocol involve incorporation of two important functionalities through cyanation and olefination in one pot under mild reaction conditions by using a less expensive Ru catalyst. The mechanism was established by isolating and characterising (using 31PNMR) an intermediate with two ortho functionalities, iminophosphorane and olefin, under specific reaction conditions. Directly functional! Cyanation and olefination was accomplished in one pot from benzoyl azides through an unprecedented directing group transformation. The method generates benzonitriles and can be used for the synthesis of 2-alkenylated benzonitrile derivatives (see scheme).

A PARTICULARLY CONVENIENT ONE-POT SYNTHESIS OF N-ALKOXYCARBONYL, N-ACYL AND N-AROYL SUBSTITUTED IMINOPHOSPHORANES; IMPROVED PREPARATION OF AZIDOFORMATES, AROYL AND ALKANOYL AZIDES; AN ALTERNATIVE ROUTE TO COMPLEX AMIDES

Chloroformates and acid chlorides react smoothly with sodium azide in acetone at 0 deg C, forming azidoformates, aroyl and alkanoyl azides in very high yield.With triphenylphosphine or other phosphines present in the reaction mixture, the forming azides are intercepted, leading directly to the corresponding N-alkanoyl, N-aroyl, N-alkoxycarbonyl, and N-aryloxycarbonyliminophosphoranes.N-acyliminophosphoranes react with n-butyllithium forming anions which react readily with electrophiles, e.g., carbonyl compounds, forming highly substituted iminophosphoranes.The phosphonium group is effortlessly removed from the latter compounds by acid hydrolysis forming the corresponding amides in high yield.Key words: Synthesis; iminophosphoranes; aroyl azides; alkanoyl azides; complex amides.