Herein, we report the first Ni-catalyzed enantioselective deaminative alkylation of amino acid and peptide derivatives with unactivated olefins. Key for success was the discovery of a new sterically encumbered bis(oxazoline) ligand backbone, thus offering a de novo technology for accessing enantioenriched sp 3 −sp 3 linkages via sp 3 C−N functionalization. Our protocol is distinguished by its broad scope and generality across a wide number of counterparts, even in the context of late-stage functionalization. In addition, an enantioselective deaminative remote hydroalkylation reaction of unactivated internal olefins is within reach, thus providing a useful entry point for forging enantioenriched sp 3 −sp 3 centers at remote sp 3 C−H sites.
With the emergence of cyber-physical systems (CPS), we are now at the brink of next computing revolution. IoT (Internet of Things) based Smart Grid (SG) is one of the foundations of this CPS revolution and defined as a power grid integrated with a large network of smart objects. The volume of time series of SG equipment is tremendous and the raw time series are very likely to contain missing values because of undependable network transferring. The problem of storing a tremendous volume of raw time series thereby providing a solid support for precise time series analytics now becomes tricky. In this paper, we propose a dependable time series analytics (DTSA) framework for IoT-based SG. Our proposed DTSA framework is capable of proving a dependable data transforming from CPS to the target database with an extraction engine to preliminary refining raw data and further cleansing the data with a correction engine built on top of a sensor-networkregularization based matrix factorization (SnrMF) method. The experimental results reveal that our proposed DTSA framework is capable of effectively increasing the dependability of raw time series transforming between CPS and the target database system through the online lightweight extraction engine and the offline correction engine. Our proposed DTSA framework would be useful for other industrial big data practices.
The first enantioselective reductive decarboxylative C(sp3)-C(sp2) cross-coupling of malonic acid derivatives are reported via the intermediacy of redox-active esters (RAEs). A newly modified chiral bis-imidazoline ligand was identified as the optimal ligand to enable this reaction, providing direct access to valuable chiral aryl esters with high efficiency and excellent enantioselectivity. Our protocol is featured by its broad scope and exceptional compatibility with a variety of functional groups, even in the context of late-stage functionalization. In addition, C(sp2)−I could be selectively functionalized with bromo(iodo)arene. The detailed mechanistic studies supported a radical based cross-coupling mechanism.
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