Photoredox Catalyzed Ring-Opening Addition Reaction Between Benzyl Bromides and Cyclic Ethers

A novel nucleophilic reaction between cyclic ethers and benzyl bromides is achieved under photoredox catalysis. The reaction proceeds through a single electron transfer (SET) pathway rather than a common SN2 mechanism. By two steps of reduction and oxidation, a benzyl bromide heterolyzes to give a carbocation and bromide ion under mild conditions, and then a cyclic ether captures both the carbocation and bromide ion to afford the addition product.

Crosslinked Fluorinated Poly(arylene Ether)s with POSS: Synthesis and Conversion to High-Performance Polymers

This study reports on a series of crosslinked poly(arylene ether)s with POSS in the main chain. The fluorinated and terminated poly(arylene ether)s were first synthesized by the nucleophilic reaction of diphenol POSS and decafluorodiphenyl monomers, including decafluorobiphenyl, decaflurobenzophenone, and decafluorodiphenyl sulfone. They were then reacted with 3-hydroxyphenyl acetylene to produce phenylacetylene-terminated poly(arylene ether)s. The polymers were of excellent processability. When heated to a high temperature, the polymers converted into a crosslinked network, exhibiting a low range of dielectric constant from 2.17 to 2.58 at 1 HMz, strong resistance against chemical solutions, low dielectric losses, and good thermal and hydrophobic properties.

Halogen Bonding in the Complexes of Brominated Electrophiles with Chloride Anions: From a Weak Supramolecular Interaction to a Covalent Br–Cl Bond

The wide-range variation of the strength of halogen bonds (XB) not only facilitates a variety of applications of this interaction, but it also allows examining the relation (and interconversion) between supramolecular and covalent bonding. Herein, the Br…Cl halogen bonding in a series of complexes of bromosubstituted electrophiles (R-Br) with chloride anions were examined via X-ray crystallographic and computational methods. Six co-crystals showing such bonding were prepared by evaporation of solutions of R-Br and tetra-n-propylammonium chloride or using Cl− anions released in the nucleophilic reaction of 1,4-diazabicyclo[2.2.2]octane with dichloromethane in the presence of R-Br. The co-crystal comprised networks formed by 3:3 or 2:2 halogen bonding between R-Br and Cl−, with the XB lengths varying from 3.0 Å to 3.25 Å. Analysis of the crystallographic database revealed examples of associations with substantially longer and shorter Br…Cl separations. DFT computations of an extended series of R–Br…Cl− complexes confirmed that the judicious choice of brominated electrophile allows varying halogen Br…Cl bond strength and length gradually from the values common for the weak intermolecular complexes to that approaching a fully developed covalent bond. This continuity of halogen bond strength in the experimental (solid-state) and calculated associations indicates a fundamental link between the covalent and supramolecular bonding.

Water soluble biguanide salts and their 1,3,5-triazine derivatives as inhibitors of acetylcholinesterase and α-glucosidase

Seven biguanide derivatives were prepared by the nucleophilic reaction between dicyandiamide and p-substitute aniline derivatives or memantine or adamantine under acidic conditions. The cyclization of the biguanide compounds were also conducted via acetone to give 1,3,5-triazine derivatives. The structures of the synthesized compounds were characterized by analytical methods. The solid state structures of [HL5]Cl, [H2L7]Cl2, [HL1a]Cl and [HL5a]Cl were investigated by X-ray diffraction study. The acetylcholinesterase and α-glucosidase inhibitor properties of the compounds were then evaluated by the spectroscopic method. The compounds were found to show considerable acetylcholinesterase and α-glucosidase inhibitory activities compared to the approved drugs. The cyclization of biguanide derivatives with acetone did not affect inhibition of acetylcholinesterase, yet increased the α-glucosidase inhibition.

Phenolphthalein polyethersulfone bearing carboxyl groups: Synthesis and its separation-membrane applications

A series of phenolphthalein polyethersulfones, containing varying contents of carboxyl groups, were synthesized via SN2 nucleophilic reaction. Structure of the prepared copolymers was confirmed by 1H NMR and FTIR. The phenolphthalein polyethersulfone comprising carboxyl groups exhibited excellent hydrophilicity and mechanical properties in the fabrication of ultrafiltration membrane. The properties of the membrane were measured using scanning electron microscopy and ultrafiltration membrane evaluator. The membrane showed superior ultrafiltration performance with a pure water flux of 399 (L·m−2·h−1), which was 1.9 times higher than that of the pristine phenolphthalein polyethersulfone. The pure water flux of the membrane with the pore-forming agent Tween 80 was up to 1082 (L·m−2·h−1), and its BSA rejection was up to 97% at 0.1 MPa. This work provided a new resin material with better performance for water treatment membrane.

Real-time monitoring of newly acidified organelles during autophagy enabled by reaction-based BODIPY dyes

Real-time monitoring of newly acidified organelles during autophagy in living cells is highly desirable for a better understanding of intracellular degradative processes. Herein, we describe a reaction-based boron dipyrromethene (BODIPY) dye containing strongly electron-withdrawing diethyl 2-cyanoacrylate groups at the α-positions. The probe exhibits intense red fluorescence in acidic organelles or the acidified cytosol while exhibiting negligible fluorescence in other regions of the cell. The underlying mechanism is a nucleophilic reaction at the central meso-carbon of the indacene core, resulting in the loss of π-conjugation entailed by dramatic spectroscopic changes of more than 200 nm between its colorless, non-fluorescent leuco-BODIPY form and its red and brightly emitting form. The reversible transformation between red fluorescent BODIPY and leuco-BODIPY along with negligible cytotoxicity qualifies such dyes for rapid and direct intracellular lysosome imaging and cytosolic acidosis detection simultaneously without any washing step, enabling the real-time monitoring of newly acidified organelles during autophagy.

Rh(III)-Catalyzed Coupling of N-Chloroimines with α-Diazo-α-Phosphonoacetates for Skeleton-Oriented Synthesis of 2H-Isoindoles

A major hurdle for realizing the full potential of transition metalcatalyzed, directed C-H functionalization synthesis of heterocycles is the blockingof ability for designated structural elaboration by the reactivity-assisting groupderived, unintended appendages. We communicate herein Rh(III)-catalyzed coupling of N-chloroimines with α-diazo-α-phosphonoacetates for skeletonoriented synthesis (SOS) of 2H-Isoindoles. Comprehensive mechanistic studies with rhodacycle intermediates support an associative covalent relay mechanism for this first reported N-chloroimine-directed C-H functionalization reaction. Theinitial dechlorination/dephosphonation under Rh(III) catalysis and subsequent deesterification under Ni(II) catalysis allow the complete elimination of unintended appendages and full exposure of reactivity for C3 and N2 ring atoms. The proofof - concept utility has been demonstrated with electrophilic substitution at the C3 site (formylation, azo derivatization) and nucleophilic reaction (methylation) at the N2 site, showcasing the enormous synthetic potential of SOS for attaching structurally unrelated appendages and enabling entry to distinct chemical space.

Rh(III)-Catalyzed Coupling of N-Chloroimines with α-Diazo-α-Phosphonoacetates for Skeleton-Oriented Synthesis of 2H-Isoindoles

A major hurdle for realizing the full potential of transition metalcatalyzed, directed C-H functionalization synthesis of heterocycles is the blockingof ability for designated structural elaboration by the reactivity-assisting groupderived, unintended appendages. We communicate herein Rh(III)-catalyzed coupling of N-chloroimines with α-diazo-α-phosphonoacetates for skeletonoriented synthesis (SOS) of 2H-Isoindoles. Comprehensive mechanistic studies with rhodacycle intermediates support an associative covalent relay mechanism for this first reported N-chloroimine-directed C-H functionalization reaction. Theinitial dechlorination/dephosphonation under Rh(III) catalysis and subsequent deesterification under Ni(II) catalysis allow the complete elimination of unintended appendages and full exposure of reactivity for C3 and N2 ring atoms. The proofof - concept utility has been demonstrated with electrophilic substitution at the C3 site (formylation, azo derivatization) and nucleophilic reaction (methylation) at the N2 site, showcasing the enormous synthetic potential of SOS for attaching structurally unrelated appendages and enabling entry to distinct chemical space.