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A general and efficient access to aryl, heteroaryl, vinyl and alkynyl difluoromethylphosphonates is described. The developed methodology using TMSCF2PO(OEt)2, iodonium salts and a copper salt provided a straightforward manifold to reach these highly relevant products. The reaction proved to be highly functional group tolerant and proceeded under mild conditions, giving the corresponding products in good to excellent yields. This method represents the first general synthetic route to this important class of fluorinated scaffolds, which are well‐recognized as in vivo stable phosphate surrogates.  相似文献   

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A versatile method for the synthesis of aryl perfluoroalkanes from arenes and aryl bromides is described. Substituted arenes or aryl bromides are converted in situ to an aryl boronate ester that readily undergoes perfluoroalkylation in air with [(phen)CuR(F)]. A broad range of aryl bromide substrates were perfluoroalkylated in good yield for the first time. [(phen)CuCF(3)] is now commercially available and has been prepared on 20?g scale.  相似文献   

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An efficient biosensor was created for the ratiometric monitoring of Cu+ and pH in the brain using both current and potential outputs. A series of N ,N ‐bis(2‐[2‐(ethylthio)ethyl])‐based (NS4s) derivatives was designed for the specific recognition of Cu+. After systematically evaluating the electrochemical parameters of Cu+ oxidation by tuning alkyl chain length, polyaromatic structure, and substitute group site of NS4, N ,N ‐bis(2‐[2‐(ethylthio)ethyl])‐2‐naphthamide (NS4‐C1) was finally optimized for Cu+ detection as it showed the most negative potential and the largest current density. At the same time, 9,10‐anthraquinone was used as a selective pH sensor with 2,2′‐azino‐bis(3‐ethylbenzthiazoline‐6‐sulfonic acid) as an internal reference. This single biosensor with both current and potential signal outputs can simultaneously determine Cu+ concentrations from 0.5 to 9.5 μm and pH values ranging from 6.0 to 8.0. The efficient biosensor was applied to the simultaneous detection of Cu+ and pH in the live brain. The average levels of Cu+ were reported for the first time in the cortex, hippocampus, and striatum in a mouse model of Alzheimer's disease.  相似文献   

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The synthesis, characterization, and C(sp2)?CF3 reductive elimination of stable aryl[tris(trifluoromethyl)]cuprate(III) complexes [nBu4N][Cu(Ar)(CF3)3] are described. Mechanistic investigations, including kinetic studies, studies of the effect of temperature, solvent, and the para substituent of the aryl group, as well as DFT calculations, suggest that the C(sp2)?CF3 reductive elimination proceeds through a concerted carbon–carbon bond‐forming pathway.  相似文献   

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1 INTRODUCTION Polymeric manganese complexes with fascinating topological chemistry have received considerable interest[1, 2]. The complexation of phen with man- ganese ion gives rise to a wide variety of coordi- nation complexes; however, (phen)Mn coordina- tion polymers are rare since the chelation of phen results in 1 to 3 5-membered chelating rings, ob- structing the way towards the coordination poly- mer. Similar situation has also been observed for 2,2?-bipyridine (bpy) which has si…  相似文献   

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Reported herein is an efficient copper(I)‐catalytic system for the diastereo‐ and enantioselective 1,2‐addition of 1,1‐bis[(pinacolato)boryl]alkanes to protected imines to afford synthetically valuable enantioenriched β‐aminoboron compounds bearing contiguous stereogenic centers. The reaction exhibits a broad scope with respect to protected imines and 1,1‐bis[(pinacolato)boryl]alkanes, thus providing β‐aminoboronate esters with excellent diastereo‐ and enantioselectivity. The synthetic utility of the obtained β‐aminoboronate ester was also demonstrated.  相似文献   

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One catalyst fits all! One catalyst is active for a wide set of benzylating reactions (see scheme). A tandem process allows the use of aldehydes and ketones as benzylating agents.

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