Divergent Reactivity of In Situ Generated Metal Azides: Reaction with N,N‐Bis(oxy)enamines as a Case Study

Abstract

What is the most significant result of this study? Non-alkali metal azides are explosive compounds, which can hardly be considered as convenient and useful reagents in organic synthesis. However,a sw ed iscovered in our study the metal ion can modulate the reactivity of the azide anion thus opening new opportunities for the synthesis of organic azides. The compromise is that the use of af ree-metal azide is not needed, since it can be safely generated in solution by ion exchange from NaN 3 and the corresponding metal salt. What was the inspiration for this cover design? The inspiration for the cover picture came from cue sports. We make an analogy of the chemical behavior observed in our studies with ab illiard game, in which balls are ions, and pockets are reac-tive centers of an organic molecule. Unlike in ar eal game based on mechanics, in a" chemical billiard", ion balls after collision may not only bounce off each other,b ut also can fuse to form ac ova-lently bonded pair,w hich moves along its own trajectory.A "metal-ion ball" depending on its nature, directs the attack of the "azide-anion ball" on either one or another electrophilic "pocket" of the substrate (silicon or carbon atoms). Thus, ac hemist is like ap rofessional billiard player selecting the right ball (promoter/cat-alyst) and disposition (reaction conditions) to hit the target center in the molecule. This simple allegory illustrates the results described in our article in ap opular and easy-to-understand manner. What other topics are you working on at the moment? Although we are originally synthetic chemists, our research interests go far beyond the borders of traditional synthesis. Besides our focus on NÀOs ystems and stereoselective synthesis, we are working in the areas of medicinal chemistry,c lick reactions, coordination compounds, polymers and quantum-chemical calculations. Our particular passions are adamantane-like molecules. Among our recent achievements are the synthesis and structural studies of "isourotropine" (the isomer of methenamine) and B,O,N-doped adamantanes. Invited for the cover of this issue is the group of Alexey Sukhorukov at the N. D. ZelinskyI nstitute of Organic Chemistry. The image depicts the reaction pathways taken by metal azides as a" chemical billiard"g ame. Read the full text of the arti

In Situ Generated Magnesium Cyanide as an Efficient Reagent for Nucleophilic Cyanation of Nitrosoalkenes and Parent Nitronates

“…Here, we suggest in situ generated magnesium cyanide [NaCN/Mg(ClO 4 ) 2 ] as a non‐volatile, soluble in DMF and cheap reagent for 1,2‐ and 1,4‐hydrocyanation reactions . It combines a nucleophilic cyanide anion and a Lewis acid (Mg 2+ ), which covalently binds to anions A preventing their degradation and can be easily removed by aqueous work‐up.…”

Addition of HO‐Acids to N,N‐Bis(oxy)enamines: Mechanism, Scope and Application to the Synthesis of Pharmaceuticals

“…In our studies, N , N ‐bis(oxy)enamines (BENAs), which are readily accessible by the silylation of nitronates or nitroalkanes, were used as model substrates (Scheme ) . BENAs possess multiple reaction sites, which can undergo reactions with protic acids.…”

Synthesis of 1,2,3‐Triazolyl‐Based Ketoximes Using Calcium Carbide as an Acetylene Source

“…Calcium carbide was purchased from Shanghai Macklin Biochemical Co. Ltd (purity: 98 %), and ground into powder prior to use. Various azide ketoximes 1a – 1t were synthesized by the reactions of the corresponding bromoketoximes with sodium azide according to literature procedures ( 1a–1h , 1j , 1k and 1m – 1t ; 1i ; 1l ). Other reagents were purchased from Energy Chemical Company (China).…”