We report a highly stereoselective synthesis of all-carbon or fluorinated tetrasubstituted alkenes from diazo reagents and fluorinated enol silyl ethers, using C-F bond as a synthetic handle. Cationic Au catalysis plays a key role in this reaction. Remarkable fluorine effects on the reactivity and selectivity was also observed.
Described here is that AuÀCCb onds showed the highest stability under biological conditions,w ith abundant thiols,a nd the best electrochemical performance compared to Au À Sand Au À Se bonds.The new finding was also confirmed by theorical calculations.B ased on this finding, as pecific molecule for recognition of Fe 2+ was designed and synthesized, and used to create as elective and accurate electrochemical sensor for the quantification of Fe 2+ .T he present ratiometric strategy demonstrates high spatial resolution for real-time tracking of Fe 2+ in ad ynamic range of 0.2-120 mM. Finally, amicroelectrode arraywith good biocompatibility was applied in imaging and biosensing of Fe 2+ in the different regions of live mouse brains.U sing this tool, it was discovered that the uptake of extracellular Fe 2+ into the cortex and striatum was largely mediated by cyclic adenosine monophosphate (cAMP) through the CREB-related pathway in the brain of am ouse with Alzheimersd isease.
A chiral secondary amine phosphoramide was developed and identified as a powerful catalyst for the Mukaiyama-Michael addition of fluorinated enol silyl ethers to tetrasubstituted olefins. The resulting products are obtained with high enantioselectivities and contain a quaternary carbon stereocenter bearing either a difluoroalkyl or monofluoroalkyl group.
A rare example of a one-pot process that involves asymmetric triple relay catalysis is reported. The key step is an asymmetric [1,5] electrocyclic reaction of functionalized ketimines. The substrates for this process were obtained in situ in a two-step process that involved the hydrogenation of nitroarenes with a Pd/C catalyst to yield aryl amines and their subsequent coupling with isatin derivatives in a Brønsted acid catalyzed ketimine formation reaction. The electrocyclization was catalyzed by a bifunctional chiral Brønsted base/hydrogen bond donor catalyst. The one-pot process gave the desired products in good yields and with excellent enantioselectivity.
The catalytic asymmetric electrophilic amination has been established as a fruitful methodology for the construction of nitrogen-bearing tetrasubstituted carbon stereocenters, with its roots nourished by the latest achievements in chiral catalysis and synthetic strategies. This review summarizes the recent progresses, briefly discusses the reaction mechanism and challenges in this context, and outlines synthetic opportunities for future development. 3 Amination Reactions Using other Amination Reagents 4 Conclusion
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