Search for: All records

We report an iridium-catalysed stereoselective cyclisation of aryl alkynes with tethered esters and imides to give silyl-protectedO,O- andN,O-acetals. 

The distribution function is essential in statistical inference and connected with samples to form a directed closed loop by the correspondence theorem in measure theory and the Glivenko-Cantelli and Donsker properties. This connection creates a paradigm for statistical inference. However, existing distribution functions are defined in Euclidean spaces and are no longer convenient to use in rapidly evolving data objects of complex nature. It is imperative to develop the concept of the distribution function in a more general space to meet emerging needs. Note that the linearity allows us to use hypercubes to define the distribution function in a Euclidean space. Still, without the linearity in a metric space, we must work with the metric to investigate the probability measure. We introduce a class of metric distribution functions through the metric only. We overcome this challenging step by proving the correspondence theorem and the Glivenko-Cantelli theorem for metric distribution functions in metric spaces, laying the foundation for conducting rational statistical inference for metric space-valued data. Then, we develop a homogeneity test and a mutual independence test for non-Euclidean random objects and present comprehensive empirical evidence to support the performance of our proposed methods. Supplementary materials for this article are available online. 

Abstract Propargylic ethers serve as useful intermediates for the synthesis of a variety of complex targets. However, propargylic substitution of prefunctionalized alkyne starting materials remains the dominant method for the synthesis of propargyl ethers, while direct etherification of simple alkynes via propargylic C−H functionalization remains largely underreported. Herein, we report an organometallic umpolung approach for iron‐mediated C−H propargylic etherification. A telescopic protocol for iron‐mediated C−H deprotonation followed by mild oxidative coupling with alcohols enabled the use of simple or functionalized alkynes for the expedient synthesis of propargylic ethers with excellent functional group compatibility, chemoselectivity and regioselectivity. 

Abstract We report a highly enantioselective intermolecular C−H bond silylation catalyzed by a phosphoramidite‐ligated iridium catalyst. Under reagent‐controlled protocols, propargylsilanes resulting from C(sp³)−H functionalization, as well the regioisomeric and synthetically versatile allenylsilanes, could be obtained with excellent levels of enantioselectivity and good to excellent control of propargyl/allenyl selectivity. In the case of unsymmetrical dialkyl acetylenes, good to excellent selectivity for functionalization at the less‐hindered site was also observed. A variety of electrophilic silyl sources (R₃SiOTf and R₃SiNTf₂), either commercial or in situ‐generated, were used as the silylation reagents, and a broad range of simple and functionalized alkynes, including aryl alkyl acetylenes, dialkyl acetylenes, 1,3‐enynes, and drug derivatives were successfully employed as substrates. Detailed mechanistic experiments and DFT calculations suggest that an η³‐propargyl/allenyl Ir intermediate is generated upon π‐complexation‐assisted deprotonation and undergoes outer‐sphere attack by the electrophilic silylating reagent to give propargylic silanes, with the latter step identified as the enantiodetermining step.