Synthetic Studies on Spirolides A and B: Formation of the Upper Carbon Framework Based on a Lewis Acid Template-Catalyzed Diels–Alder Reaction

The upper fragment of spirolides A and B, which are marine phycotoxins that exhibit strong antagonistic activities on nicotinic acetylcholine receptors, was constructed. The functionalized cyclohexene in spirolides was stereoselectively synthesized from the bicyclic lactone, which could be readily accessed by the Lewis acid template-catalyzed asymmetric Diels–Alder reaction of the pentadienol and methyl acrylate.     

A Bait-and-Switch Method for the Construction of Artificial Esterases for Substrate-Selective Hydrolysis

Outcomes of chemical reactions are generally dominated by the intrinsic reactivities of reaction partners, but enzymes frequently override such constraints to transform less reactive molecules in the presence of more reactive ones. Despite the attractiveness of such catalysis, it is difficult to build synthetic catalysts with these features. Micellar imprinting is a powerful method to create template-complementary binding sites inside protein-sized water-soluble nanoparticles. When a photocleavable functional monomer was used to bind two phosphonate/phosphate templates as transition-state analogues, active sites with predetermined size and shape were formed inside doubly cross-linked micelles through molecular imprinting. Postmodification replaced the binding group with a catalytic pyridyl group, forming highly selective artificial esterases. The catalysts displayed enzyme-like kinetics and turnover numbers that were in the hundreds. The selectivity of the catalysts, derived from the substrate-complementary imprinted active sites, enabled transformation of less reactive esters in the presence of more reactive ones.     

Synergistic Surface Passivation of CH3NH3PbBr3 Perovskite Quantum Dots with Phosphonic Acid and (3-Aminopropyl)triethoxysilane

CH₃NH₃PbBr₃ perovskite quantum dots (PQDs) are synthesized by using four different linear alkyl phosphonic acids (PAs) in conjunction with (3-aminopropyl)triethoxysilane (APTES) as capping ligands. The resultant PQDs are characterized by means of XRD, TEM, Raman spectroscopy, FTIR spectroscopy, UV/Vis, photoluminescence (PL), time-resolved PL, and X-ray photoelectron spectroscopy (XPS). PA chain length is shown to control the PQD size (ca. 2.9–4.2 nm) and excitonic absorption band positions (λ=488–525 nm), with shorter chain lengths corresponding to smaller sizes and bluer absorptions. All samples show a high PL quantum yield (ca. 46–83 %) and high PL stability; this is indicative of a low density of band gap trap states and effective surface passivation. Stability is higher for smaller PQDs; this is attributed to better passivation due to better solubility and less steric hindrance of the shorter PA ligands. Based on the FTIR, Raman, and XPS results, it is proposed that Pb²⁺ and CH₃NH₃⁺ surface defects are passivated by R−PO₃²⁻ or R−PO₂(OH)⁻, whereas Br⁻ surface defects are passivated by R−NH₃⁺ moieties. This study establishes the combination of PA and APTES ligands as a highly effective dual passivation system for the synergistic passivation of multiple surface defects of PQDs through primarily ionic bonding.     

Alkoxide-Promoted Selective Hydroboration of N-Heteroarenes: Pivotal Roles of in situ Generated BH3 in the Dearomatization Process

While numerous organo(metallic)catalyst systems were documented for dearomative hydroboration of N-aromatics, alkoxide base catalysts have not been disclosed thus far. Described herein is the first example of alkoxide-catalyzed hydroboration of N-heteroaromatics including pyridines, providing a broad range of reduced N-heterocycles with high efficiency and selectivity. Mechanistic studies revealed an unprecedented counterintuitive dearomatization pathway, in which 1) pyridine-BH₃ adducts undergo a hydride attack by alkoxyborohydrides, 2) in situ generated BH₃ serves as a catalytic promoter, and 3) 1,4-dihydropyridyl borohydride is in a predominant resting state.     

E- and Z-Proxamidines,Unprecedented 1,3-Diazacyclooct-1-ene Alkaloids from Fruiting Bodies of Laccaria proxima

Fruiting bodies of Laccaria proxima were screened for the presence of new secondary metabolites by means of HPLC-UV and LC-HR-(+)-ESIMS. Thus, two isomeric alkaloids with a highly unusual core structure, E-proxamidine and its Z-isomer, were isolated from Laccaria proxima. The proxamidines consist of an eight-membered heterocyclic ring system with a formamidine unit. The structures were established by 2D NMR spectroscopic methods, HR-(+)-ESIMS, and HR-(+)-ESIMS/MS. The proxamidines are probably biosynthetically derived from tryptophan, dimethylallyl pyrophosphate, and S-adenosylmethionine and the eight-membered ring of the proxamidines is likely to be generated by a rearrangement of the tryptophan sceleton. Metabolic profiling of fruiting bodies of some other Laccaria species revealed that the proxamidines appear in significant amounts only in L. proxima making the compounds suitable as chemotaxonomic markers. E-Proxamidine exhibits herbicidal activity against Lepidium sativum.     

Mono-Heteroatom Substitution for Harnessing Excited-State Structural Planarization of Dihydrodibenzo[a,c]phenazines

With the aim of generalizing the structure–properties relationship of bending heterocyclic molecules that undergo prominent photoinduced structural planarization (PISP), a series of new dihydrodibenzo[ac]phenazine derivatives in which one nitrogen atom is replaced by oxygen ( PNO ), sulfur ( PNS ), selenium ( PNSe ), or dimethylmethanediyl ( PNC ) was strategically designed and synthesized. Compounds PNO , PNS , and PNSe have significantly nonplanar geometries in the ground state, which undergo PISP to give a planarlike conformer and hence a large emission Stokes shift. A combination of femtosecond early relaxation dynamics and computational approaches established an R*→I* (intermediate)→P* sequential kinetic pattern for PNS and PNSe , whereas PNO undergoes R*→P* one-step kinetics. The polarization ability of the substituted heteroatoms, which is in the order O<S<Se, correlates with their increase in π conjugation, and hence the Stokes shift of the emission is in the order PNO < PNS < PNSe . Compound PNSe with the largest PISP barrier was shown to be a highly sensitive viscosity probe. Further evidence for heteroatom-harnessing PISP is given by PNC , in which the dimethylmethanediyl substituent lacks lone pair electrons for π extension, showing the normal emission of the bent structure. The results led to the conclusion that PISP is ubiquitous in dihydrodibenzo[ac]phenazines, for which the driving force is elongation of the π delocalization to gain stabilization in the excited state.     

Resonance Energy Transfer in a Genetically Engineered Polypeptide Results in Unanticipated Fluorescence Intensity

The fluorescence intensity of a C-terminal acceptor chromophore, N-(7-dimethylamino-4-methyl coumarin (DACM), increased proportionally with 280 nm irradiation of an increasing number of donor tryptophan residues located on a β-sheet forming polypeptide. The fluorescence intensity of the acceptor chromophore increased even as the length of the β-sheet edge approached 256 Å, well beyond the Förster radius for the tryptophan–acceptor chromophore pair. The folding of the peptides under investigation was verified by circular dichroism (CD) and deep UV resonance Raman experiments. Control experiments showed that the enhancement of DACM fluorescence occurred concomitantly with peptide folding. In other control experiments, the DACM fluorescence intensity of the solutions of tryptophan and DACM did not show any enhancement of DACM fluorescence with increasing tryptophan concentrations. Formation of fibrillar aggregates of the substrate peptides prepared for the fluorescence studies was undetectable by thioflavin T (ThT) fluorescence.     

Total Synthesis of Callyspongiolide,Part 2: The Ynoate Metathesis/cis-Reduction Strategy

The macrocyclic core of the cytotoxic marine natural product callyspongiolide ( 1 ) was forged by ring-closing alkyne metathesis (RCAM) of an ynoate precursor using a molybdenum alkylidyne complex endowed with triarylsilanolate ligands as the catalyst. This result is remarkable in view of the failed attempts documented in the literature at converting electron deficient alkynes with the aid of more classical catalysts. The subsequent Z-selective semi-reduction of the resulting cycloalkyne by hydrogenation over nickel boride required careful optimization in order to minimize overreduction and competing dehalogenation of the compound's alkenyl iodide terminus as needed for final attachment of the side chain of 1 by Sonogashira coupling. The required cyclization precursor itself was prepared via Kocienski olefination.     

Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

The topology of the molecular electron density of benzene dithiol gold cluster complex Au₄−S−C₆H₄−S′−Au′₄ changed when relativistic corrections were made and the structure was close to a minimum of the Born–Oppenheimer energy surface. Specifically, new bond paths between hydrogen atoms on the benzene ring and gold atoms appeared, indicating that there is a favorable interaction between these atoms at the relativistic level. This is consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied. In addition to relativistic effects, here, we establish the sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization.     

Synthesis and Structure Determination of SCM-15: A 3D Large Pore Zeolite with Interconnected Straight 12×12×10-Ring Channels

A new germanosilicate zeolite named SCM-15 (Sinopec Composite Material No. 15), the first zeolite containing a 3-dimensional (3D) channel system with interconnected 12-, 12-, and 10-ring channels (pore sizes: 6.1×7.2, 6.1×7.4, and 5.2×5.9 Å), has been synthesized using neutral 4-pyrrolidinopyridine as organic structure-directing agents (OSDAs). Its structure has been determined by combining single-crystal electron diffraction (SCED) and synchrotron powder X-ray diffraction (SPXD) data. The unique open framework structure of SCM-15 is related to that of FOS-5 ( BEC ), ITQ-7 ( ISV ), PKU-16 ( POS ), ITQ-26 ( IWS ), ITQ-21, Beta polymorph B, and SU-78B, since all these framework structures can be constructed from similar chains which are connected through shared 4-ring or double 4-ring (d4r) units. Based on this relation, six topologically reasonable 3D large or extra-large pore hypothetical zeolites are predicted.