Preparation Of β-azido Ketone And α-diazo-β-amino Ketone From α,β-unsaturated Ketones Without Catalyst

Organic azides play an irreplaceable role in chemical biology and drug discovery,and they are also versatile intermediates in organic chemistry and materials science.At the same time,the diazo group is also one of the most widely used functional groups in synthetic chemistry.In addition to being a 1,3-dipole with higher reactivity,the diazo group itself can also be converted into a variety of reactive intermediates,including cations,vinyl cations,and free and metal-bound carbenes.However,it is still an arduous challenge to develop a method that is universally effective and can introduce azide and diazo groups at specific sites under mild conditions.In recent years,many research groups have developed a series of methods to synthesize azides or diazoniums with nitrogen and phosphorus-containing ligands.Although these methods can efficiently obtain a certain target product,they are costly and cannot be selectively controlled product.In this paper,a simple and practical method was developed for obtaining fluorinated β-azido ketones and β-amino-α-diazocarbonyl compounds from β-fluoroalkyl α,β-unsaturated ketones without catalyst based on previous work.The production of the target product can be adjusted simply by changing the solvent and temperature.Experimental investigations have shown that the solvent plays a major role in the control process.After investigating the unsaturated ketone as the reaction substrate,it is found that the substrate has a wide range of versatility,and the target product can be obtained with high yield.And can complete the gram-scale preparation with high yield,and the resulting product also shows extremely wide practicability in later applications.It can easily complete the synthesis of "click chemistry" conversion of triazole,and obtain the reduced product with equivalent yield.In this paper,a series of control experiments are carried out to explore the mechanism of the conversion of 2a to 3a,and finally a possible solvent-controlled conversion mechanism is proposed.