Near-infrared upper phenyl-fused BODIPY as a photosensitizer for photothermal-photodynamic therapy.

The introduction of a ring-fused segment into a BODIPY scaffold promoted a spectral bathochromic-shift and enhanced the intersystem crossing capability by a twisted structure. In this work, we designed and synthesized an upper ring-fused BODIPY with 4-dimethylaminostyryl groups (BBDP), which had excellent optical performance for photothermal-photodynamic therapy.

Effects of dehydroepiandrosterone (DHEA) supplementation on cortisol, leptin, adiponectin, and liver enzyme levels: A systematic review and meta-analysis of randomised clinical trials.

Background And Aims: Dehydroepiandrosterone (DHEA) supplementation has been investigated in patients with altered cortisol levels and is proposed to ameliorate the metabolic profile related to adipose tissue. However, further research is warranted and evidence is no compelling for liver safety. Hence, we aimed to meta-analyse the effects of DHEA supplementation on circulating levels of cortisol, liver enzymes, and adipokines.

An improved synthesis of telmisartan the copper-catalyzed cyclization of -haloarylamidines.

A concise synthetic route was designed for making telmisartan. The key bis-benzimidazole structure was constructed the copper-catalyzed cyclization of -haloarylamidines. By adopting this approach, telmisartan was obtained in a 7-step overall yield of 54% starting from commercially available 3-methyl-4-nitrobenzoic acid, and the use of HNO/HSO for nitration and polyphosphoric acid (PPA) for cyclization in the reported literatures were avoided.

Synthesis of CBD and Its Derivatives Bearing Various C4'-Side Chains with a Late-Stage Diversification Method.

A novel synthetic route for making (-)-CBD and its derivatives bearing various C4'-side chains is developed by a late-stage diversification method. Starting from commercially available phloroglucinol, the key intermediate (-)-CBD-2OPiv-OTf is efficiently and regioselectively prepared and further undergoes Negishi cross-coupling to furnish (-)-CBD. This approach allowed an efficient synthesis of (-)-CBD in a five-step total 52% yield on a 10 g scale.

Synthesis and Properties of a Bay-Annulated-Indigo Tetramer Based on Low-Cost Spiro[Fluorene-9,9'-Xanthene] Core.

A three-dimensional bay-annulated-indigo (BAI) tetramer has been prepared by appending BAI units onto a low-cost spiro[fluorene-9,9'-xanthene] (SFX) core. The target compound 4BAI-SFX exhibits strong and broad absorption in the visible region covering the range of 450~700 nm. The electrochemical measurement illuminates the characteristics of a deep lowest unoccupied molecular orbital (LUMO) level and multiple redox states of 4BAI-SFX.

Oxidative Aromatization of 3,4-Dihydroquinolin-2(1 H)-ones to Quinolin-2(1 H)-ones Using Transition-Metal-Activated Persulfate Salts.

Inorganic persulfate salts were identified as efficient reagents for the oxidative aromatization of 3,4-dihydroquinolin-2(1 H)-ones through the activation of readily available transition metals, such as iron and copper. The feasible protocol conforming to the requirement of green chemistry was utilized in the preparation of the key intermediate (7-(4-chlorobutoxy)quinolin-2(1 H)-one 2) of brexpiprazole in 80% isolated yield on a 100 g scale, and different quinolin-2(1 H)-one derivatives with various functional groups were demonstrated in 52-89% yields.

Charge-patching method for the calculation of electronic structure of polypeptides.

Theoretical study of the electronic structures of protein is a fundamental challenge in computational biochemistry due to the large size of the systems. The electronic structure of a protein is important for some of the important protein functionalities, such as photosynthesis. In this study, we explored the charge-patching method to calculate the electronic structure of polypeptides.

A new water-soluble phosphorus-dipyrromethene and phosphorus-azadipyrromethene dye: PODIPY/aza-PODIPY.

PODIPY and aza-PODIPY have been successfully prepared by the treatment of dipyrromethene and azadipyrromethene with POCl3 in the presence of Et3 N. The new PODIPY and aza-PODIPY dyes are found to have photophysical properties. PODIPY and aza-PODIPY are water-soluble, and aza-PODIPY is suited for labeling living Hep-2 cells for imaging assays in the near-infrared region.

Formal ring-opening/cross-coupling reactions of 2-pyrones: iron-catalyzed entry into stereodefined dienyl carboxylates.

Open access: Despite the exceptional level of sophistication in cross-coupling chemistry, reactions of substrates that incorporate the leaving group as an integral part into a heterocyclic scaffold are scarce. The title reaction outlines the utility of this reaction format (see scheme; acac=acetylacetonate), provides a convenient entry into stereodefined diene carboxylates, and adds a new chapter to the field of iron catalysis.

Neocuproine-KOtBu promoted intramolecular cross coupling to approach fused rings.

Polycycles can be produced with different linkages (A, B = O, N, C, S) by constructing biaryl C-C bonds via neocuproine-KO(t)Bu promoted cross coupling between C-Xs and C-Hs.

Transition-metal-catalyzed C-C bond formation through the fixation of carbon dioxide.

Carbon dioxide is an important carbon source in the atmosphere and is "problematic" toward the activities of human beings. Although carbon dioxide is a cheap, abundant and relatively nontoxic C1 source, its chemical transformations have not been widely developed so far and are still far from synthetic applications, especially in the construction of the C-C bond. This critical review summarizes the recent advances on transition-metal-catalyzed C-C bond formation through the fixation of carbon dioxide and their synthetic applications (124 references).

Activation of "inert" alkenyl/aryl C-O bond and its application in cross-coupling reactions.

Enol and phenol functionalities are very common in organic molecules. Utilization of these materials is very appealing in organic synthesis because they are important alternatives to organohalides in cross-coupling reactions. In this review, we summarize the transition-metal-catalyzed cross-coupling of enol- and phenol-based electrophiles, including phosphates, sulfonates, ethers, carboxylates, and phenolates.

New strategy to construct fused/bridged/spiro carbocyclic scaffolds based on the design of novel 6-C synthon precursor.

In this article we report a new strategy to build fused/spiro/bridged carbocyclic systems with a novel 6-C synthon from readily available diallyl diacetates through the sequential Pd-catalyzed double allyl alkylation and Diels-Alder annulation. Further exploration on the application of this strategy can construct useful complex scaffolds.

Palladium-catalyzed cross-coupling of polyfluoroarenes with simple arenes.

The most efficient method to construct biaryls is the direct dehydrogenative cross-coupling of two different aromatic rings. Such an ideal cross arylation starting from distinct polyfluoroarenes and simple arenes was presented. The selectivity of the cross-coupling was controlled by both of the electronic property of fluoroarenes and steric hindrance of simple arenes.

An efficient organocatalytic method for constructing biaryls through aromatic C-H activation.

The direct functionalization of C-H bonds has drawn the attention of chemists for almost a century. C-H activation has mainly been achieved through four metal-mediated pathways: oxidative addition, electrophilic substitution, σ-bond metathesis and metal-associated carbene/nitrene/oxo insertion. However, the identification of methods that do not require transition-metal catalysts is important because methods involving such catalysts are often expensive.

Pd-catalyzed oxidative coupling with organometallic reagents via C-H activation.

Direct selective palladium catalyzed C-H functionalization has become a highly attractive strategy in organic synthesis and represents a highly desirable goal. Compared with cross-coupling reactions of C-H bonds with aryl or alkyl halides/pseudohalides, the strategy of cross-coupling reactions of C-H bonds with organometallic reagents is of great significance and obvious advantages. This feature article provides a comprehensive summary of recent advances and an intensive analysis on Pd-catalyzed C-H activation and oxidative coupling with various organometallic reagents.

Pd-catalyzed C-H functionalizations of O-methyl oximes with arylboronic acids.

Useful methods have been developed to construct ortho-arylated aryl aldoximes, aryl ketoximes, and fluorenones via Pd(II)-catalyzed direct C-H arylation by using arylboronic acids as arylating reagents based on the analysis of the pathways of direct functionalization of aryl aldoximes.

A scheme for rapid prediction of cooperativity in hydrogen bond chains of formamides, acetamides, and N-methylformamides.

A scheme is proposed in this article to predict the cooperativity in hydrogen bond chains of formamides, acetamides, and N-methylformamides. The parameters needed in the scheme are derived from fitting to the hydrogen bonding energies of MP2/6-31+G** with basis set superposition error (BSSE) correction of the hydrogen bond chains of formamides containing from two to eight monomeric units. The scheme is then used to calculate the individual hydrogen bonding energies in the chains of formamides containing 9 and 12 monomeric units, in the chains of acetamides containing from two to seven monomeric units, in the chains of N-methylformamides containing from two to seven monomeric units.

Investigation on the individual contributions of N-H...O=C and C-H...O=C interactions to the binding energies of beta-sheet models.

In this article, the binding energies of 16 antiparallel and parallel beta-sheet models are estimated using the analytic potential energy function we proposed recently and the results are compared with those obtained from MP2, AMBER99, OPLSAA/L, and CHARMM27 calculations. The comparisons indicate that the analytic potential energy function can produce reasonable binding energies for beta-sheet models. Further comparisons suggest that the binding energy of the beta-sheet models might come mainly from dipole-dipole attractive and repulsive interactions and VDW interactions between the two strands.