Development of α‑Borylmethyl‑(<i>Z</i>)‑crotylboronate Reagent and Enantioselective Syntheses of (<i>E</i>)‑δ-Hydroxymethyl-<i>syn</i>-homoallylic Alcohols via Highly Stereoselective Allylboration

We report herein the development of α-borylmethyl-(Z)-crotylboronate reagent and the application in highly stereo- and enantioselective syntheses of (E)-δ-hydroxymethyl-syn-homoallylic alcohols. Starting from 1,4-pentadiene, α-borylmethyl-(Z)-crotylboronate was synthesized in two steps with high Z-selectivity and enantioselectivity. Subsequent aldehyde allylboration with the developed boron reagent gave highly enantioenriched (E)-δ-hydroxymethyl-syn-homoallylic alcohols upon oxidative workup

Asymmetric Syntheses of (<i>E</i>)‑δ-Hydroxymethyl-<i>anti</i>-homoallylic Alcohols via Highly Enantio- and Stereoselective Aldehyde Allylation with α‑Borylmethyl‑(<i>E</i>)‑crotylboronate

Highly stereo- and enantioselective synthesis of (E)-δ-hydroxymethyl-anti-homoallylic alcohols is reported. Under the developed conditions, reactions between aldehydes and chiral nonracemic α-borylmethyl-(E)-crotylboronate upon oxidative workup gave δ-hydroxymethyl-anti-homoallylic alcohols with high E-selectivities and enantioselectivities

Solvent-Free DABCO-Mediated [3 + 2] Cycloadditions of Donor–Acceptor Cyclopropanes with Aldehydes: Strategy for Synthesis of Fully Substituted Furans

DABCO-mediated [3 + 2] cycloadditions of donor–acceptor cyclopropanes with aldehydes under solvent-free conditions have been developed for the preparation of fully substituted furans which are a wide range of structurally interesting and pharmacologically significant compounds. The reaction appears to be general for a variety of 1-cyano­cyclo­propane-1-carboxylates and aldehydes and tolerates the presence of aromatic moieties with electron-withdrawing and electron-donating substituents

Table_1_Causal association of immune cells and polycystic ovarian syndrome: a Mendelian randomization study.xlsx

BackgroundPolycystic ovarian syndrome (PCOS) is a common reproductive disorder that affects a considerable number of women worldwide. It is accompanied by irregular menstruation, hyperandrogenism, metabolic abnormalities, reproductive disorders and other clinical symptoms, which seriously endangers women’s physical and mental health. The etiology and pathogenesis of PCOS are not completely clear, but it is hypothesized that immune system may play a key role in it. However, previous studies investigating the connection between immune cells and PCOS have produced conflicting results.MethodsMendelian randomization (MR) is a powerful study design that uses genetic variants as instrumental variables to enable examination of the causal effect of an exposure on an outcome in observational data. In this study, we utilized a comprehensive two-sample MR analysis to examine the causal link between 731 immune cells and PCOS. We employed complementary MR methods, such as the inverse-variance weighted (IVW) method, and conducted sensitivity analyses to evaluate the reliability of the outcomes.ResultsFour immunophenotypes were identified to be significantly associated with PCOS risk: Memory B cell AC (IVW: OR [95%]: 1.123[1.040 to 1.213], p = 0.003), CD39+ CD4+ �4+ (IVW: OR [95%]: 0.869[0.784 to 0.963], p = 0.008), CD20 on CD20- CD38-(IVW: OR [95%]:1.297[1.088 to 1.546], p = 0.004), and HLA DR on CD14- CD16+ monocyte (IVW: OR [95%]:1.225[1.074 to 1.397], p = 0.003). The results of the sensitivity analyses were consistent with the main findings.ConclusionsOur MR analysis provides strong evidence supporting a causal association between immune cells and the susceptibility of PCOS. This discovery can assist in clinical decision-making regarding disease prognosis and treatment options, and also provides a new direction for drug development.</p

Solvent-Free DABCO-Mediated [3 + 2] Cycloadditions of Donor–Acceptor Cyclopropanes with Aldehydes: Strategy for Synthesis of Fully Substituted Furans

DABCO-mediated [3 + 2] cycloadditions of donor–acceptor cyclopropanes with aldehydes under solvent-free conditions have been developed for the preparation of fully substituted furans which are a wide range of structurally interesting and pharmacologically significant compounds. The reaction appears to be general for a variety of 1-cyano­cyclo­propane-1-carboxylates and aldehydes and tolerates the presence of aromatic moieties with electron-withdrawing and electron-donating substituents

Solvent-Free DABCO-Mediated [3 + 2] Cycloadditions of Donor–Acceptor Cyclopropanes with Aldehydes: Strategy for Synthesis of Fully Substituted Furans

DABCO-mediated [3 + 2] cycloadditions of donor–acceptor cyclopropanes with aldehydes under solvent-free conditions have been developed for the preparation of fully substituted furans which are a wide range of structurally interesting and pharmacologically significant compounds. The reaction appears to be general for a variety of 1-cyano­cyclo­propane-1-carboxylates and aldehydes and tolerates the presence of aromatic moieties with electron-withdrawing and electron-donating substituents

Asymmetric Syntheses of (<i>Z</i>)- or (<i>E</i>)‑β,γ-Unsaturated Ketones via Silane-Controlled Enantiodivergent Catalysis

Cu-catalyzed highly stereoselective and enantiodivergent syntheses of (Z)- or (E)-β,γ-unsaturated ketones from 1,3-butadienyl silanes are developed. The nature of the silyl group of the dienes has a significant impact on the stereo- and enantioselectivity of the reactions. Under the developed catalytic systems, the reactions of acyl fluorides with phenyldiemthylsilyl-substituted 1,3-diene gave (Z)-β,γ-unsaturated ketones bearing an α-tertiary stereogenic center with excellent enantioselectivities and high Z-selectivities, where the reactions with triisopropylsilyl-substituted 1,3-butadiene formed (E)-β,γ-unsaturated ketones with high optical purities and excellent E-selectivities. The products generated from the reactions contain three functional groups with orthogonal chemical reactivities, which can undergo a variety of transformations to afford synthetically valuable intermediates

Molecular Stacking Dependent Molecular Oxygen Activation in Supramolecular Polymeric Photocatalysts

Here, we showed that supramolecular assemblies based on perylene diimides (PDIs) are able to activate molecular oxygen through both the electron transfer and energy transfer pathways, which consequently leads to the formation of superoxide radicals (·O2–) and singlet oxygen species (1O2), respectively. These reactive oxygen species (ROS) can effectively lead to oxidative coupling of benzylamine and oxidation of 2-chloroethyl sulfide (CEES). We have designed and synthesized PDIs with similar molecular structures yet differing by the molecular stacking modes. We found that the photooxidation activities of the PDI supramolecular assemblies are inversely associated with the photoluminescence wavelength difference between the assemblies and the monomers (Δλ) quantitatively, and a smaller Δλ results in a higher catalytic efficiency accordingly. Overall, this work contributes to the design and fabrication of high performance photocatalysts based on metal-free organic materials