Functional kupffer cells migrate to the liver from the intraperitoneal cavity.

We established a method of KC transplantation by intraperitoneal (i.p.) injection using EGFP-expressing cells (EGFP-KCs) and normal KCs.

Borenium-Catalyzed Reduction of Pyridines through the Combined Action of Hydrogen and Hydrosilane.

Mesoionic carbene-stabilized borenium ions efficiently reduce substituted pyridines to piperidines in the presence of a hydrosilane and a hydrogen atmosphere. Control experiments and deuterium labeling studies demonstrate reversible hydrosilylation of the pyridine, enabling full reduction of the N-heterocycle under milder conditions. The silane is a critical reaction component to prevent adduct formation between the piperidine product and the borenium catalyst.

Inhibitory effects of cyanidin-3-O-glucoside in black soybean hull extract on RBL-2H3 cells degranulation and passive cutaneous anaphylaxis reaction in mice.

Black soybean hull extract (BSHE) exhibits a variety of biological activities. However, little is known about the effects of BSHE on immunoglobulin E (IgE)-mediated type I allergic reactions. The anti-allergic effect of BSHE was assessed with the degranulation assay using rat basophilic leukemia RBL-2H3 cells and the passive cutaneous anaphylaxis (PCA) reaction in mice.

Ru(CO)-Catalyzed Reaction of 1,6-Diynes, Carbon Monoxide, and Water via the Reductive Coupling of Carbon Monoxide.

We report the ruthenium-catalyzed cyclization of 1,6-diynes with two molecules of carbon monoxide and water to give a variety of catechols. This reaction likely proceeds through the intermediacy of the water-gas shift reaction to generate an yne-diol-type intermediate followed by a [4 + 2] cycloaddition with 1,6-diynes. The reaction requires no external reductants or hydride sources and provides a novel and valuable method for the synthesis of a variety of catechols.

Alkyltriflones in the Ramberg-Bäcklund Reaction: An Efficient and Modular Synthesis of -Difluoroalkenes.

The unprecedented synthesis of -difluoroalkenes through the Ramberg-Bäcklund reaction of alkyl triflones is described herein. Structurally diverse, fully substituted -difluoroalkenes that are difficult to prepare by other methods can be easily prepared from readily available triflones by treatment with specific Grignard reagents. Experimental and computational studies provide insight into the unique and critical role of the Grignard reagent, which serves both as a base to remove the α-proton and as a Lewis acid to assist C-F bond activation.

Chemoselective and Stereoselective Alcoholysis of Binaphthyl Phosphonothioates: Straightforward Access to Both Stereoisomers of Biologically Relevant -Stereogenic Phosphonothioates.

-Stereogenic phosphonothioates have attracted great attention due to their potent biological activities as analogues of phosphoric acids and phosphorothioates. We demonstrate here straightforward access to stereogenic phosphonothioates through the use of binaphthyl phosphonothioates as a chiral template. The first-step alcoholysis of binaphthyl phosphonothioates proceeded via a transfer of the axial chirality of a binaphthyl group to the central chirality of a phosphorus atom to give only monoalcohol adducts with moderate to excellent diastereoselectivities.

Modular synthesis of α-fluorinated arylmethanes via desulfonylative cross-coupling.

α-Fluoromethylarenes are common substructures in pharmaceuticals and agrochemicals, with the introduction of fluorine often resulting in improved biological activity and stability. Despite recent progress, synthetic routes to α-fluorinated diarylmethanes are still rare. Herein we describe the Pd-catalyzed Suzuki-Miyaura cross-coupling of α-fluorinated benzylic triflones with arylboronic acids affording structurally diverse α-fluorinated diarylmethanes.

Pyridine-catalyzed desulfonative borylation of benzyl sulfones.

Herein, we report the transition-metal free, pyridine-catalyzed desulfonative borylation of benzyl sulfones with bis(pinacolato)diboron (B2pin2). A variety of benzhydryl- and benzyl boronic esters could be synthesized from readily prepared sulfone derivatives. The borylation of cyclic sulfones accompanied by ring opening also proceeded to afford the corresponding sulfonate, which could be converted into functionalized sulfones and sulfonamides.

Hydrolysis of Phosphonothioates with a Binaphthyl Group: P-Stereogenic O-Binaphthyl Phosphonothioic Acids and Their Use as Optically Active Ligands and Chiral Discriminating Agents.

The hydrolysis of phosphonothioates with a binaphthyl group afforded the first example of O-(2'-hydroxy)binaphthyl phosphonothioic acids in good to high yields and >95:5 diastereoselectivity. The reaction proceeds via an axis-to-center chirality-transfer reaction. The ability of these acids to act as chiral molecular auxiliaries was demonstrated by using them as optically active ligands for the asymmetric ethylation of benzaldehyde and as a chiral discriminating agent for chiral aliphatic amines.

Preparation of Quaternary Centers via Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling of Tertiary Sulfones.

We describe the development of a nickel-catalyzed Suzuki-Miyaura cross-coupling of tertiary benzylic and allylic sulfones with arylboroxines. A variety of tertiary sulfones, which can easily be prepared via a deprotonation-alkylation route, were reacted to afford symmetric and unsymmetric quaternary products in good yields. We highlight the use of either BrettPhos or Doyle's phosphines as effective ligands for these challenging desulfonative coupling reactions.

Employing BINOL-Phosphoroselenoyl Chloride for Selective Inositol Phosphorylation and Synthesis of Glycosyl Inositol Phospholipid from Entamoeba histolytica.

The chemical synthesis of glycosyl inositol phospholipids from Entamoeba histolytica is reported. The key feature of this synthesis is a regioselective phosphorylation reaction that occurs through desymmetrization of a myo-inositol derivative with phosphoroselenoyl chloride. A new protecting-group strategy was developed that utilizes allyl and alloc groups to synthesize complex glycolipids bearing unsaturated lipids.

Sequential Deprotonation-Alkylation of Binaphthyloxy-Substituted Phosphonochalcogenoates: Chiral Tri- and Tetrasubstituted Carbon Centers Adjacent to a Phosphorus Atom.

Sequential deprotonation and alkylation of 1,1'-binaphthyloxy-substituted phosphonoselenoates and phosphonates resulted in the diastereoselective formation of chiral tri- and tetrasubstituted carbon centers adjacent to a phosphorus atom.

Iterative protecting group-free cross-coupling leading to chiral multiply arylated structures.

The Suzuki-Miyaura cross-coupling is one of the most often utilized reactions in the synthesis of pharmaceutical compounds and conjugated materials. In its most common form, the reaction joins two sp(2)-functionalized carbon atoms to make a biaryl or diene/polyene unit. These substructures are widely found in natural products and small molecules and thus the Suzuki-Miyaura cross-coupling has been proposed as the key reaction for the automated assembly of such molecules, using protecting group chemistry to affect iterative coupling.

Fluorinative hydrolysis of phosphorothioic acid esters with a binaphthyl group through axis-to-center chirality transfer leading to the formation of P-chiral phosphorothioic monofluoridic acid salts.

Asymmetric synthesis of P-chiral phosphorothioic monofluoridic acid ammonium salts was achieved via axis-to-center chirality transfer reactions by using phosphorothioic acid O-esters with a binaphthyl group, and the absolute stereochemistry of the salts was determined by X-ray analyses and by comparison of their CD spectra.

Anti-Markovnikov hydrophosphoroselenoylation of alkenes using phosphorodiselenoic acid esters leading to the formation of phosphonoselenoic acid esters.

Phosphorodiselenoic acid esters with a binaphthyl group were reacted with alkenes in the presence of Bu3SnH and AIBN to give phosphonoselenoic acid esters in moderate to good yields. The addition of a phosphoroselenoyl group to alkenes proceeded in an anti-Markovnikov fashion. The diastereoselectivity was improved by the introduction of substituents to 3,3'-positions of a binaphthyl group.