scholarly journals Preparation and Reactions of Polyfunctional Magnesium and Zinc Organometallics in Organic Synthesis

2021 ◽  
Author(s):  
Alexander Kremsmair ◽  
Johannes H. Harenberg ◽  
Kuno Schwärzer ◽  
Andreas Hess ◽  
Paul Knochel
Keyword(s):  
Organic Synthesis ◽  
Organic Halides ◽  
Metal Insertion

Polyfunctional organometallics of magnesium and zinc are readily prepared from organic halides via a direct metal insertion in the presence of LiCl or a Br/Mg-exchange using iPrMgCl·LiCl (turbo-Grignard) or related...

scholarly journals Homolytic substitution at phosphorus for C–P bond formation in organic synthesis

2013 ◽  
Vol 9 ◽  
pp. 1269-1277 ◽  
Author(s):  
Hideki Yorimitsu
Keyword(s):  
Organic Chemistry ◽  
Organic Synthesis ◽  
Organophosphorus Compounds ◽  
Bond Formation ◽  
Review Article ◽  
Organic Halides ◽  
Carbon Centered Radical ◽  
Synthetic Approaches ◽  
Homolytic Substitution

Organophosphorus compounds are important in organic chemistry. This review article covers emerging, powerful synthetic approaches to organophosphorus compounds by homolytic substitution at phosphorus with a carbon-centered radical. Phosphination reagents include diphosphines, chalcogenophosphines and stannylphosphines, which bear a weak P–heteroatom bond for homolysis. This article deals with two transformations, radical phosphination by addition across unsaturated C–C bonds and substitution of organic halides.

scholarly journals Photoelectrocatalytic C–H halogenation over an oxygen vacancy-rich TiO2 photoanode

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Zhenhua Li ◽  
Lan Luo ◽  
Min Li ◽  
Wangsong Chen ◽  
Yuguang Liu ◽  
...  
Keyword(s):  
Oxygen Vacancy ◽  
Organic Synthesis ◽  
Separation Efficiency ◽  
Theoretical Data ◽  
Chloride Ions ◽  
Photoelectrochemical Cells ◽  
Halide Ions ◽  
Organic Halides ◽  
Self Powered ◽  
Tio2 Photoanode

AbstractPhotoelectrochemical cells are emerging as powerful tools for organic synthesis. However, they have rarely been explored for C–H halogenation to produce organic halides of industrial and medicinal importance. Here we report a photoelectrocatalytic strategy for C–H halogenation using an oxygen-vacancy-rich TiO2 photoanode with NaX (X=Cl−, Br−, I−). Under illumination, the photogenerated holes in TiO2 oxidize the halide ions to corresponding radicals or X2, which then react with the substrates to yield organic halides. The PEC C–H halogenation strategy exhibits broad substrate scope, including arenes, heteroarenes, nonpolar cycloalkanes, and aliphatic hydrocarbons. Experimental and theoretical data reveal that the oxygen vacancy on TiO2 facilitates the photo-induced carriers separation efficiency and more importantly, promotes halide ions adsorption with intermediary strength and hence increases the activity. Moreover, we designed a self-powered PEC system and directly utilised seawater as both the electrolyte and chloride ions source, attaining chlorocyclohexane productivity of 412 µmol h−1 coupled with H2 productivity of 9.2 mL h−1, thus achieving a promising way to use solar for upcycling halogen in ocean resource into valuable organic halides.

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