Transient carbonyl nitrenes RC(O)N, formed during thermal-or photoinduced decomposition of carbonyl azides RC(O)N3, are highly liable to the Curtius rearrangement, producing isocyanates RNCO in almost quantitative yield. Contrary to common belief, we found a thermally persistent triplet carbonyl nitrene, FC (
The dipolar oxathiazyne-like sulfinylnitrene RS(O)N, a highly reactive α-oxo nitrene, has been rarely investigated. Upon flash vacuum pyrolysis of sulfinyl azide CF3S(O)N3 at 350 °C, an elusive sulfinylnitrene CF3S(O)N was generated in the gas phase in its singlet ground state and was characterized by matrix-isolation IR spectroscopy. Further fragmentation of CF3S(O)N at 600 °C produced CF3 and a novel iminyl radical OSN, an SO2 analogue, which were unambiguously identified by IR spectroscopy. Consistent with the experimental observations, DFT calculations clearly support a stepwise decomposition mechanism of CF3S(O)N3.
Electroorganic synthesis is an emerging area of high impact research in organic chemistry, which is considered as one of the green and efficient methods and attracts growing research attention. In this review, we summarized comprehensively the recent literature reports on the electrochemical oxidative difunctionalization of unsaturated C-C bonds. The reaction types described in this review included electrochemical intermolecular cyclization, electrochemical intramolecular cyclization, and electrochemical difunctionalization of alkenes/alkynes. This review focuses on the discussion of its synthetic generality for the preparation of functionalized compounds and the related electrochemical oxidative reaction mechanism. Dr. Haibo Mei (left) obtained his B.Sc. in 2009 and Ph.D. in 2014 in organic chemistry from Nanjing University. Then he joined Nanjing University as a research fellow in the area of asymmetric synthesis. In 2017, he moved to Nanjing Forestry University and became an associate professor there. Zizhen Yin (middle) obtained his B.Sc. from Nanjing Forestry University in 2018. He is currently a third-year graduate student in the research group of Professor Han at Nanjing Forestry University. Professor Jianlin Han (right) received his Ph. D. in organic Chemistry in 2007 from Nanjing University. He then carried out postdoctoral studies for one year at Texas Tech University. In 2008, he moved to the University of Oklahoma to continue postdoctoral research for nearly one year. In 2009, he took the position of Associate Professor at the Nanjing University. In 2018, he moved to Nanjing Forestry University and became a professor there. Scheme 5 Ruthenium-catalyzed dehydrogenative cyclization reaction of N-pyrimidyl anilines Scheme 6 Electrochemical dehydrogenative cyclization of alkynes with N-substituted arylamides Chin.
Compositing stimuli-responsive polymers or microgels can provide material systems with the unique capability of being programmable under specific external signals. Herein we show that by using CO2-responsive microgels as carriers of metal nanocatalysts and stabilizers to disperse the immiscible liquid organic hydrogen carriers (LOHCs), organosilanes in water coreagents, we can achieve a programmable generation of hydrogen for safe and portable applications of hydrogen fuels. The solubility of the tertiary amine-based microgel particles in water can be switched through CO2 bubbling or vacuuming, allowing a controllable demulsification or emulsification of the LOHCs/water system. Microcompartments consisting of a porous microgel shell with nanocatalysts and organosilane droplets can be broken and created on demand, resulting in a change of the oil/water interfacial area of over 3 orders of magnitude and a hydrogen generation rate increase of about 20-fold by forming the microcompartments. In addition, it was demonstrated that successive breaking/creating of the microcompartments can minimize the effect of the inevitable ripening and coalescence of oil droplets in the emulsion, providing a 3-fold increase in reaction rate. The microgels/nanocatalysts also show good stability and durability in repeated runs of the hydrogen generation. It is possible that controllably creating/breaking of the microcompartments containing smart microgels or polymer shells could become an important strategy to power up programmable or intelligent systems in the future.
Synthesis of block cationic polyacrylamides (CPAMs) by introducing random CPAM as both chain-transfer agent and stabilizer for aqueous RAFT dispersion polymerization of acrylamide is a promising approach for engineering high-performance CPAMs.
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