Double C–H Functionalization of Indoles via Three-Component Reactions/CuCl₂‑Catalyzed Aerobic Dehydrogenative Coupling for the Synthesis of Polyfunctional Cyclopenta[<i>b</i>]indoles

A sequential Rh₂(OAc)₄-catalyzed multicomponent reaction and CuCl₂-catalyzed postcyclization process is developed to build polyfunctional cyclopenta­[<i>b</i>]­indoles in good yields with high diastereoselectivities in an atom- and step-economic fashion. The key discovery in this process is the CuCl₂-catalyzed intramolecular aerobic dehydrogenative Csp²–Csp² cross-coupling of indole C2 with an enol functionality. Mechanistic studies including X-ray photoelectron spectroscopy analysis suggest that the catalytic cycle involves Cu­(II) and Cu­(I). This coupling reaction represents a unique example of aerobic Cu-catalyzed direct coupling of indoles with enols under mild conditions

Rh(II)/Brønsted Acid Cocatalyzed Intramolecular Trapping of Ammonium Ylides with Enones: Diastereoselective Synthesis of 2,2,3-Trisubstituted Indolines

Highly diastereoselective intramolecular trapping of ammonium ylides with enones has been developed through a Rh­(II)/Brønsted acid cocatalytic strategy. This process allows rapid and efficient construction of <i>N</i>-unprotected polyfunctional 2,2,3-trisubstituted indolines in moderate to good yields with excellent diastereoselectivity

Cascade Reaction of Propargyl Amines with AgSCF₃, as Well as One-Pot Reaction of Propargyl Amines, AgSCF₃, and Di-<i>tert</i>-butyl Peroxide: Access to Allenyl Thiocyanates and Allenyl Trifluoromethylthioethers

An efficient cascade reaction of propargyl amines with AgSCF₃ and KBr is developed, affording allenyl thiocyanates at room temperature in high yields. This transformation proceeds via the in situ formation of isothiocyanate intermediates, followed by a [3,3]-sigmatropic rearrangement. The resulting allenyl thiocyanates bearing 3-(electro-donating phenyl) substitutions without isolation can then be reacted with di-<i>tert</i>-butyl peroxide and AgSCF₃ under reflux to generate novel allenyl trifluoromethylthioether compounds in moderate to good yields via a “one-pot” three-step process

Data_Sheet_1_Presence of Segmented Filamentous Bacteria in Human Children and Its Potential Role in the Modulation of Human Gut Immunity.docx

<p>Segmented filamentous bacteria (SFB) are commensal organisms that grow by anchoring a specialized holdfast structure to the intestinal walls of a variety of animals. Interaction of SFB with Peyer’s patches in mice promotes the post-natal maturation of the immune system. We previously reported that the colonization of SFB in humans mainly occurs by 36 months of age, and is difficult to be detected afterward. In this study, we measured the level of SFB in intestinal fluids of human children. SFB were found via qPCR to represent a small fraction of the whole SFB-positive microbiota (10⁵ SFB in 10¹¹ total bacteria). Bacteria with filamentous segmented morphology were observed in intestinal fluids via fluorescent in situ hybridization, and from gut biopsies via scanning electron microscopy. SFB-specific DNA and peptide fragments were also identified via multiple displacement amplification PCR and mass spectrometry. There was an overall positive correlation between the presence of SFB and the titer of total secretory immunoglobulin A (sIgA), which is more apparent in intestinal fluids of the age group of 8–36 months. Afterward there was a decline of SFB in numbers correlated with a reduction of total sIgA. RT-qPCR analysis of the terminal ileal biopsies revealed that the expression of Th17 pathway genes were induced in SFB-positive samples, while the markers of T and B cell receptor signaling pathways were also upregulated. Collectively, these data suggest that SFB is a rare member of microbiota, and may play an important role in the development of human gut immunity.</p