Search

An ambimodal transition state (TS) that leads to formation of four different pericyclic reaction products ([4 + 6]-, [2 + 8]-, [8 + 2]-, and [6 + 4]-cycloadducts) without any intervening minima has been designed and explored with DFT computations and quasiclassical molecular dynamics. Direct dynamics simulations propagated from the ambimodal TS show the evolution of trajectories to give the four cycloadducts. The topography of the PES is a key factor in product selectivity. A good correlation is observed between geometrical resemblance of the products to the ambimodal TS (measured by the RMSD) and the ratio of products formed in the dynamics simulations, We are grateful to the National Science Foundation (CHE1764328 to K.N.H.) for financial support of this research and for access to XSEDE and UCLA Hoffman 2 for computer time and for this study. A.M.S. thanks the Madrid Government (Comunidad de Madrid-Spain) under the Multiannual Agreement with Universidad Autónoma de Madrid in the line Support to Young Researchers, in the context of the V PRICIT (SI3-PJI-2021-00463) and “Ministerio de Educación Cultura y Deporte” for funding (CAS18/00458)

Lignin valorization is being intensely pursued via tandem catalytic depolymerization and biological funneling to produce single products. In many lignin depolymerization processes, aromatic dimers and oligomers linked by carbon–carbon bonds remain intact, necessitating the development of enzymes capable of cleaving these compounds to monomers. Recently, the catabolism of erythro -1,2-diguaiacylpropane-1,3-diol ( erythro -DGPD), a ring-opened lignin-derived β-1 dimer, was reported in Novosphingobium aromaticivorans . The first enzyme in this pathway, LdpA (formerly LsdE), is a member of the nuclear transport factor 2 (NTF-2)-like structural superfamily that converts erythro -DGPD to lignostilbene through a heretofore unknown mechanism. In this study, we performed biochemical, structural, and mechanistic characterization of the N. aromaticivorans LdpA and another homolog identified in Sphingobium sp. SYK-6, for which activity was confirmed in vivo. For both enzymes, we first demonstrated that formaldehyde is the C 1 reaction product, and we further demonstrated that both enantiomers of erythro -DGPD were transformed simultaneously, suggesting that LdpA, while diastereomerically specific, lacks enantioselectivity. We also show that LdpA is subject to a severe competitive product inhibition by lignostilbene. Three-dimensional structures of LdpA were determined using X-ray crystallography, including substrate-bound complexes, revealing several residues that were shown to be catalytically essential. We used density functional theory to validate a proposed mechanism that proceeds via dehydroxylation and formation of a quinone methide intermediate that serves as an electron sink for the ensuing deformylation. Overall, this study expands the range of chemistry catalyzed by the NTF-2-like protein family to a prevalent lignin dimer through a cofactorless deformylation reaction.

A late-stage photoisomerization/cyclization union tactic, in conjunction with Type I Anion Relay Chemistry (ARC), permits enantioselective total syntheses and then biological evaluation of (+)-peniciketals A and B. The photochemical protocol was further showcased by an efficient three-step construction of the architecturally complex polycyclic skeleton found in (-)-diocollettines A. The mechanism and diastereoselectivity of the photochemical protocol have also been explored by both experiment and density functional theory calculations.

Here we report a nonenzymatic glycosylation reaction that builds axial S-glycosidic bonds under biorelevant conditions. This strategy is enabled by the design and use of allyl glycosyl sulfones as precursors to glycosyl radicals and exploits the exceptional functional group tolerance of radical processes. Our method introduces a variety of unprotected glycosyl units to the cysteine residues of peptides in a highly selective fashion. Through developing the second-generation protocol, we applied our method in the direct glycosylation of complex polypeptides and proteins. Computational studies were performed to elucidate the reaction mechanism.

New enzyme catalysts are usually engineered by repurposing the active sites of natural proteins. Here we show that design and directed evolution can be used to transform a non-natural, functionally naive zinc-binding protein into a highly active catalyst for an abiological hetero-Diels–Alder reaction. The artificial metalloenzyme achieves >104 turnovers per active site, exerts absolute control over reaction pathway and product stereochemistry, and displays a catalytic proficiency (1/KTS = 2.9 × 1010 M−1) that exceeds all previously characterized Diels–Alderases. These properties capitalize on effective Lewis acid catalysis, a chemical strategy for accelerating Diels–Alder reactions common in the laboratory but so far unknown in nature. Extension of this approach to other metal ions and other de novo scaffolds may propel the design field in exciting new directions. A de novo designed zinc-binding protein has been converted into a highly active, stereoselective catalyst for a hetero-Diels–Alder reaction. Design and directed evolution were used to effectively harness Lewis acid catalysis and create an enzyme more proficient than other reported Diels–Alderases.

The biosynthesis of pyrroindomycins A and B features a complexity-building [4 + 2] cycloaddition cascade, which generates the spirotetramate core under the catalytic effects of monofunctional Diels-Alderases PyrE3 and PyrI4. We recently showed that the main functions of PyrI4 include acid catalysis and induced-fit/conformational selection. We now present quantum mechanical and molecular dynamics studies implicating a different mode of action by PyrE3, which prearranges an anionic polyene substrate into a high-energy reactive conformation at which an inverse-electron-demand Diels-Alder reaction can occur with a low barrier. Stereoselection is realized by strong binding interactions at the endo stereochemical relationship and a local steric constraint on the endo-1,3-diene unit. These findings, illustrating distinct mechanisms for PyrE3 and PyrI4, highlight how nature has evolved multiple ways to catalyze Diels-Alder reactions.

We studied the mechanisms of activation and stereoselectivity of a monofunctional Diels-Alderase (PyrI4)-catalyzed intramolecular Diels-Alder reaction that leads to formation of the key spiro-tetramate moiety in the biosynthesis of the pyrroindomycin family of natural products. Key activation effects of PyrI4 include acid catalysis and an induced-fit mechanism that cooperate with the unique "lid" feature of PyrI4 to stabilize the Diels-Alder transition state. PyrI4 enhances the intrinsic Diels-Alder stereoselectivity of the substrate and leads to stereospecific formation of the product.

The mechanism of the redox-neutral organocatalytic Mitsunobu reaction, catalyzed by (2-hydroxybenzyl)diphenylphosphine oxide, reported by Denton et al., has been studied computationally with ωB97X-D density functional theory. We discovered that the nucleophilic substitution reaction between carboxylate and alkoxyphosphonium ions, to reform the phosphine oxide catalyst, is the rate-determining step of the overall process and is significantly accelerated compared with a general-acid-catalyzed SN2 reaction. The (2-hydroxybenzyl)diphenylphosphine oxide is regenerated and activated in every catalytic cycle via intramolecular dehydration/cyclization. We also designed several phosphine oxide catalysts that we predict to be more effective catalysts.

A phytochemical investigation of the MeOH extract of the leaves and twigs of Amentotaxus argotaenia, a relict vulnerable coniferous species endemic to China, led to the isolation and characterization of 35 diterpenoids/norditerpenoids. Twenty of these are new, including 11 ent-kaurane-type (amentotaxins C-M, 1-11, respectively), three icetexane-type [= 9(10→20)abeo-abietane-type (amentotaxins N-P, 12-14, respectively)], four ent-labdane-type (amentotaxins Q-T, 15-18, respectively), and two isopimarane-type [amentotaxins U (19) and V (20)] compounds. Their structures were elucidated on the basis of spectroscopic data, single-crystal X-ray diffraction, the modified Mosher's method, and electronic circular dichroism data analyses. Compounds 1-9 are rare 18-nor-ent-kaurane-type diterpenoids featuring a 4β,19-epoxy ring. All the isolates were evaluated for their cytotoxic effects against a small panel of cultured human cancer cell lines (HeLa, A-549, MDA-MB-231, SKOV3, Huh-7, and HCT-116), and some of them exhibited cytotoxicities with IC50 values ranging from 1.5 to 10.0 μM.

Here we report a nonenzymatic glycosylation reaction that builds axial

The chemistry of carbohydrates has a history of over 100 years, but simple, stereoselective and efficient glycosylation methods remain highly needed to facilitate the studies of sugars in various disciplines. Here we report a strategy for 1,2-cis-glycosylation without using metals, strong (Lewis) acids, elaborate catalysts or labile substrates. Our method operates by a unique mechanism: it activates glycosyl donors through a radical cascade rather than the conventional acid-promoted, ionic process. As elucidated by computational and experimental studies, the allyl glycosyl sulfones (as donors) form halogen bond complexes with perfluoroalkyl iodides, which-merely by visible light irradiation-fragment via radical intermediates to give the electrophilic glycosyl iodides. In situ trapping by various nucleophiles affords, in a stereoconvergent manner, the challenging 1,2-cis-glycosides. This metal- and acid-free reaction shows remarkable tolerance to functional groups. The high stereoselectivity holds for a broad array of donors. This study suggests that the simple C2-alkoxy group can serve as an effective directing group for building 1,2-cis-glycosidic bonds.

Reforestation is an effective way to alleviate deforestation and its negative impacts on ecosystem services. In tropical rainforest ecosystem, however, frequent typhoons and heavy rainfall can result in landslides and uprooting of many seedlings, making reforestation efforts very difficult, especially within extremely degraded sites where soil conditions cannot support any plant life. Here, we described a reforestation protocol which is based on tropical rainforest successional processes to not only prevent landslides and tree uprooting due to frequent typhoon and heavy rain, but also accelerate tropical forest succession. This protocol first used the slope and soil layer of the undisturbed old-growth tropical rainforest as a reference to reconstruct slope and soil layers. Then multiple tropical tree species with high growth and survival rate were separately monocultured in the reconstructed soil layers. In the year of 2015 and 2016, we tested the effectiveness of this protocol to recover a 0.2 km2 extremely degraded tropical rainforest which consists of bare rock and thus does not support any plant life, in Sanya city, China. Our results showed that, both typhoons and heavy rains did not result in landslide or any tree damages in the area this reforestation protocol was used. Moreover, our separately monocultured eight fast-growing tree species have much higher fast-growing related functional traits than those for tree species in the adjacent undisturbed tropical seasonal forest, which in turn resulted in large soil water and nutrient loss within 3 years. This seemed to simulate a quick transition from primary succession (consist of bare rock and cannot support any plant life) to mid-stage of secondary tropical rainforest succession (many fast-growing pioneer tree species induced high soil water and nutrient loss). Thus, mixing the late-successional tropical tree species with each of the separately monocultured eight fast-growing tree species can accelerate recovery to the undisturbed tropical rainforest as soon as possible. Overall, based on tropical rainforest successional processes, our research provides an effective protocol for quickly and effectively restoring an extremely degraded tropical rainforest ecosystem. We expect that this work will be important for the future recovery of other extremely degraded tropical rainforest ecosystems.

Lycopodium alkaloids (LAs) are the characteristic metabolites of club mosses. Chemical differences often exist in different specimens of a single plant species collected from different geographic origins. In this study, a preliminary LC-MS detection and dereplication analyses of alkaloidal constituents of Lycopodium cernuum var. sikkimense (Mull. Hal.) C.B. Clarke (LCVS2) collected from Fujian province led to the isolation and characterization of three undescribed LAs, lycocernuskines A-C, and six known cernuane-type LAs. The known compounds were previously isolated from the same plant species (LCVS1) collected from Chongqing, and so their dereplication in LCVS2 was accomplished based on their retention times (tR) and the quasi-molecular ion peaks in the LC-MS fingerprint. Chemical structures were identified by spectroscopic methods, single-crystal X-ray diffraction analysis, and electronic circular dichroism calculations. Lycocernuskines A and B are the first two examples of C-12 hydroxylated phlegmarane-type LAs bearing a nitrone residue at the quinoline ring. The isolates were evaluated for their anti-AChE and neuroprotective effects.

We report here the orchestration of molecular ion networking and a set of computationally assisted structural elucidation approaches in the discovery of a new class of pyrroloiminoquinone alkaloids that possess selective bioactivity against pancreatic cancer cell lines. Aleutianamine represents the first in a new class of pyrroloiminoquinone alkaloids possessing a highly strained multibridged ring system, discovered from Latrunculia ( Latrunculia) austini Samaai, Kelly & Gibbons, 2006 (class Demospongiae, order Poecilosclerida, family Latrunculiidae) recovered during a NOAA deep-water exploration of the Aleutian Islands. The molecule was identified with the guidance of mass spectrometry, nuclear magnetic resonance, and molecular ion networking (MoIN) analysis. The structure of aleutianamine was determined using extensive spectroscopic analysis in conjunction with computationally assisted quantifiable structure elucidation tools. Aleutianamine exhibited potent and selective cytotoxicity toward solid tumor cell lines including pancreatic cancer (PANC-1) with an IC50 of 25 nM and colon cancer (HCT-116) with an IC50 of 1 μM, and represents a potent and selective candidate for advanced preclinical studies.

Monoterpene indole alkaloids are a large class of natural products derived from a single biosynthetic precursor, strictosidine. We describe a synthetic approach to strictosidine that relies on a key facially selective Diels-Alder reaction between a glucosyl-modified alkene and an enal to set the C15-C20-C21 stereotriad. DFT calculations were used to examine the origin of stereoselectivity in this key step, wherein two of 16 possible isomers are predominantly formed. These calculations suggest the presence of a glucosyl unit, also inherent in the strictosidine structure, guides diastereoselectivity, with the reactive conformation of the vinyl glycoside dienophile being controlled by an exo-anomeric effect. (-)-Strictosidine was subsequently accessed using late-stage synthetic manipulations and an enzymatic Pictet-Spengler reaction. Several new natural product analogs were also accessed, including precursors to two unusual aryne natural product derivatives termed "strictosidyne" and "strictosamidyne". These studies provide a strategy for accessing glycosylic natural products and a new platform to access monoterpene indole alkaloids and their derivatives.

To provide spectroscopic data for lowly charged tungsten ions relevant to fusion research, this work focuses on the ${\mathrm{W}}^{8+}$ ion. Six visible spectra lines from ${\mathrm{W}}^{8+}$ in the range of 420--660 nm are observed with a compact electron-beam ion trap in Shanghai. Furthermore, transition energies are calculated for the 30 lowest levels of the $4{f}^{14}5{s}^{2}5{p}^{4}, 4{f}^{13}5{s}^{2}5{p}^{5}$, and $4{f}^{12}5{s}^{2}5{p}^{6}$ configurations of ${\mathrm{W}}^{8+}$ by using the flexible atomic code (fac) and grasp package. Reasonably good agreement is found between our two independent atomic-structure calculations. The resulting atomic parameters are adopted to simulate the spectra based on the collisional-radiative model implemented in the fac code. This assists us with identification of six strong magnetic-dipole transitions in the $4{f}^{13}5{s}^{2}5{p}^{5}$ and $4{f}^{12}5{s}^{2}5{p}^{6}$ configurations from our experiments.

A chemical modification study was conducted on the marine natural product aaptamine (1), isolated from the marine sponge Aaptos aaptos. Thirty new derivatives substituted by various aromatic rings at the 3- and 7-positions of aaptamine were prepared by bromination, followed by the Suzuki coupling reaction. Sixteen compounds displayed cytotoxicities to four cancer cell lines (IC50 < 10 μM). In particular, compound 5i demonstrated a significant antiproliferative effect on the extranodal natural killer/T-cell lymphoma (ENKT) cell line SNK-6 with an IC50 value of 0.6 μM. Additionally, compound 5i showed cytotoxicities to multiple lymphoma cell lines, including Ramos, Raji, WSU-DLCL2, and SU-DHL-4 cells.

All living organisms synthesize phospholipids as the primary constituent of their cell membranes. Enzymatic synthesis of diacylphospholipids requires preexisting membrane-embedded enzymes. This limitation has led to models of early life in which the first cells used simpler types of membrane building blocks and has hampered integration of phospholipid synthesis into artificial cells. Here we demonstrate an enzyme-free synthesis of natural diacylphospholipids by transacylation in water, which is enabled by a combination of ion pairing and self-assembly between lysophospholipids and acyl donors. A variety of membrane-forming cellular phospholipids have been obtained in high yields. Membrane formation takes place in water from natural alkaline sources such as soda lakes and hydrothermal oceanic vents. When formed vesicles are transferred to more acidic solutions, electrochemical proton gradients are spontaneously established and maintained. This high-yielding non-enzymatic synthesis of natural phospholipids in water opens up new routes for lipid synthesis in artificial cells and sheds light on the origin and evolution of cellular membranes.

A phytochemical investigation of the MeOH extract of the leaves and twigs of

We report the genome-guided discovery of sungeidines, a class of microbial secondary metabolites with unique structural features. Despite evolutionary relationships with dynemicin-type enediynes, the sungeidines are produced by a biosynthetic gene cluster (BGC) that exhibits distinct differences from known enediyne BGCs. Our studies suggest that the sungeidines are assembled from two octaketide chains that are processed differently than those of the dynemicin-type enediynes. The biosynthesis also involves a unique activating sulfotransferase that promotes a dehydration reaction. The loss of genes, including a putative epoxidase gene, is likely to be the main cause of the divergence of the sungeidine pathway from other canonical enediyne pathways. The findings disclose the surprising evolvability of enediyne pathways and set the stage for characterizing the intriguing enzymatic steps in sungeidine biosynthesis. Submitted/Accepted version

A unified synthetic strategy leading to the total synthesis of (−)-nodulisporic acids D, C, and B is described. Key synthetic transformations include a nickel-chromium mediated cyclization, an aromatic ring functionalization employing a novel copper-promoted alkylation, a palladium-catalyzed cross coupling cascade/indole ring construction, and a palladium-mediated regio- and diastereoselective allylic substitution/cyclization reaction, the latter to construct ring-D.

A copper-catalyzed site-selective propargylation/allenylation reaction toward carbonyl compounds has been mechanistically investigated using a computational approach. Different reaction pathways and catalytic cycles were investigated. Control of the site selectivity arises from a destabilizing interaction introduced by the phenyl-substituted ligand.

Indole terpenes have attracted the interests of synthetic chemists due to their complex architectures and potent biological activities. Examples of total syntheses of several indole terpenes were reviewed in this article to honor Professor K.C. Nicolaou.

One new bourbonane-type ( 1 ) and one new cadinane-type ( 2 ) sesquiterpenoids, along with one known aromodendrane-type ( 3 ) and five known megastigmane-type ( 4 – 8 ) compounds, were isolated from the leaves and twigs of Manglietia aromatica , a Chinese endangered plant that has not been previously phytochemically investigated. The structures and absolute configurations of the new isolates, (1 R ,4 S ,5 S ,6 S ,7 S, 10 S )-4-hydroxy-bourbon-8-one ( 1 ) and (1 R ,6 S ,7 S )-1-hydroxy- cadin-4,9-dien-8-one ( 2 ), were established by means of spectroscopic methods and a combination of experimental and calculated electronic circular dichroism (ECD). Among the isolates, compound 2 was found to show a moderate inhibitory effect against the human protein tyrosine phosphatase 1 B (PTP1B) enzyme, a target for the treatment of type-II diabetes and obesity, with an IC 50 value of 83.5 μM.

Formation mechanism of ${\mathrm{H}}_{3}^{+}$ ions from doubly charged hydrocarbons ($\mathrm{C}{\mathrm{H}}_{4}$ and ${\mathrm{C}}_{2}{\mathrm{H}}_{4}$) is investigated by combining charged particle (300 eV electrons and 3 keV/u ${\mathrm{Ar}}^{8+}$ ions) collision experiments and quantum chemistry calculations. The kinetic energy release (KER) distribution for each ${\mathrm{H}}_{3}^{+}$ loss process was measured with the cold target recoil ion momentum spectroscopy. The good agreement between the mean KER and corresponding theoretical reverse activation energy, related to a transition state and the asymptote of the dissociation products, provides information on the ${\mathrm{H}}_{3}^{+}$ formation dynamics. A ${\mathrm{H}}_{2}$ roaming mechanism is proposed for the formation of ${\mathrm{H}}_{3}^{+}$. Since the hydrocarbons in the interaction with charged particles have direct interests in astronomical environments, the finding of this work would be helpful in the understanding of the energetics and dynamics of ${\mathrm{H}}_{3}^{+}$ formation in space.

Three-fragment dissociation dynamics of ${\mathrm{C}}_{2}{\mathrm{H}}_{2}{}^{2+}$ dications and ${\mathrm{C}}_{2}{\mathrm{H}}_{2}{}^{3+}$ trications induced by electron capture of slow (3-keV/u) ${\mathrm{Ar}}^{8+}$ ions are investigated. Using cold target recoil ion momentum spectroscopy, the complete kinematic information and thus kinetic energy releases are determined for the three-fragment channels, ${\mathrm{C}}_{2}{\mathrm{H}}_{2}{}^{2+}\ensuremath{\rightarrow}{\mathrm{H}}^{+}+{\mathrm{C}}_{2}{}^{+}+\mathrm{H}$ and ${\mathrm{C}}_{2}{\mathrm{H}}_{2}{}^{3+}\ensuremath{\rightarrow}{\mathrm{H}}^{+}+{\mathrm{C}}_{2}{}^{+}+{\mathrm{H}}^{+}$. Then by analyzing the complete kinematics with a Dalitz plot and Newton diagram, different fragmentations, i.e., concerted or sequential pathway, are identified. For dications, the sequential fragmentation ${\mathrm{C}}_{2}{\mathrm{H}}_{2}{}^{2+}\ensuremath{\rightarrow}{\mathrm{H}}^{+}+{\mathrm{C}}_{2}{\mathrm{H}}^{+}\ensuremath{\rightarrow}{\mathrm{H}}^{+}+{\mathrm{C}}_{2}{}^{+}+\mathrm{H}$ is dominant. However, the trications mainly dissociate via the synchronous concerted fragmentation. The sequential pathway ${\mathrm{C}}_{2}{\mathrm{H}}_{2}{}^{3+}\ensuremath{\rightarrow}{\mathrm{H}}^{+}+{\mathrm{C}}_{2}{\mathrm{H}}^{2+}\ensuremath{\rightarrow}{\mathrm{H}}^{+}+{\mathrm{C}}_{2}{}^{+}+{\mathrm{H}}^{+}$, which was found to be significant at higher collision velocities, is not observed here. This distinction reveals the important role of projectile velocity on the fragmentation dynamics for some specific channels.

DFT exploration of 1,5- and 1,6-hydrogen atom transfers (HAT), radical addition, and relay to alkene is reported. The reactivity of 1,5- and 1,6-HAT are similar. We also explored reactions involving a multiple radical transferring process. Initially generated radicals undergo a multiple HAT process to form multiple bonds in a “relay” fashion, provided by exquisitely balanced rates.

The (3+2) cycloadditions between electron-deficient Pd-oxyallyls and conjugated dienes have been investigated with density functional theory calculations. A stepwise mechanism with C-C bond formation occurring first is supported by computations. The key electron-withdrawing ester substituent on the Pd-oxyallyl species decreases the migratory insertion barrier by both lowering the LUMO energy and enabling a less-strained six-membered coordination mode. The lack of (3+2) reactivity with monoenes is attributed to higher migratory insertion barriers due to a lower-energy HOMO, as well as high C-O reductive elimination barriers, which become rate-determining. Conjugated dienes enable the formation of a highly electrophilic η3 Pd-allyl species and greatly facilitates C-O formation.

In this work, visible and extreme ultraviolet spectra of ${\mathrm{W}}^{7+}$ are measured using the high-temperature superconducting electron-beam ion trap (EBIT) at the Shanghai EBIT Laboratory under extremely low-energy conditions (lower than the nominal electron-beam energy of 130 eV). The relevant atomic structure is calculated using the flexible atomic code package based on the relativistic configuration interaction method. The grasp2k code, in the framework of the multiconfiguration Dirac-Hartree-Fock method, is employed as well for calculating the wavelength of the M1 transition in the ground configuration of ${\mathrm{W}}^{7+}$. A line from the ${\mathrm{W}}^{7+}$ ions is observed at a little higher electron-beam energy than the ionization potential for ${\mathrm{W}}^{4+}$, making this line appear to be from ${\mathrm{W}}^{5+}$. A hypothesis for the charge-state evolution of ${\mathrm{W}}^{7+}$ is proposed based on our experimental and theoretical results; that is, the occurrence of ${\mathrm{W}}^{7+}$ ions results from indirect ionization caused by stepwise excitation between some metastable states of lower-charge-state W ions, at the nominal electron-beam energy of 59 eV.

Visible-light-induced generation of dithianyl and dioxolanyl radicals via selective hydrogen atom transfer (HAT) has been achieved. This radical relay tactic enables remote C(sp(3))—H functionalization to permit rapid access to polyol and spiroketal segments, and in turn has been exploited as a key synthetic construct in the total synthesis of the danshenspiroketallactones. The conformational stability of the danshenspiroketallactones has also been defined via experiments and DFT calculations.

Six undescribed Lycopodium alkaloids (LAs) comprising four lycodine-type (lycofargesiines A–D), one lycopodine-type (lycofargesiine E), and a phlegmarine-type (lycofargesiine F), together with 16 known ones were isolated from the club moss Huperzia fargesii. Their structures and absolute configurations were determined by extensive spectroscopic methods, electronic circular dichroism (ECD) analysis, and density functional theory (DFT) calculations. (7S,8R,12R,13R)-Lycofargesiine A is a rare naturally occurring LA possessing an exocyclic double bond between C-15 and C-16, with ring A being a rare 2,3-dihyropyridone motif. Lycofargesiine D is an uncommon lycodine-type alkaloid featuring a unique N-acetylated tetrahydropyridinyl segment (ring A), whereas lycofargesiine F is the first phlegmarane-type LA bearing two nitrone moieties. In addition to the isolated huperzine A in this study, another two isolates (lycofargesiine C and 16-hydroxyhuperzine A) were also found to show inhibitory activities against acetylcholinesterase (AChE), with IC50 values of 8.63 and 5.18 μM, respectively.

The absolute electron capture cross sections for single and double charge exchanges (CEs) between the highly charged ion O6+ and CO2, CH4, H2, and N2, the dominant collision processes in the solar wind, have been measured in the energies from 7 keV · q (2.63 keV u−1) to 52 keV · q (19.5 keV u−1). These measurements were carried out in the new experimental instrument setup at Fudan University, and the errors of the cross sections for single and double CEs at the 1σ confidence level were about 11% and 16%, respectively. Limited agreement is achieved with single electron capture results calculated by the classical overbarrier model. These cross section data are useful for the simulation of ion–neutral processes in astrophysical environments and to improve the present theoretical model of fundamental atomic processes.

Four fawcettimine-type (palhicerines A-D, resp.) and two lycopodine-type (palhicerines E and F) Lycopodium alkaloids together with twenty known ones were isolated from the whole plant of Palhinhaea cernua. The structures and absolute configurations of the palhicerines A-F were determined by extensive spectroscopic methods, single-crystal X-ray diffraction analyses, chemical transformation, and electronic circular dichroism (ECD) calculations or induced electronic circular dichroism (IECD) spectra. Among the isolates, the new C/D-ring of the palhicerines A-C (trans-fused fawcettimine-type alkaloids) are rare, and each possesses a β-oriented C-16 methyl group and a distinctive tertiary methoxy group at C-13. Chemotaxonomy for differentiating species in the genus Palhinhaea is briefly discussed.

One novel (named palcernuine, 1) and five known cernuane-type (2–6) alkaloids were isolated from the whole plant of Palhinhaea cernua f. sikkimensis. The structure of 1, possessing an unprecedented [5/6/6/6]-tetracyclic ring system containing two nitrogen atoms, was established on the basis of spectroscopic methods, and its absolute configuration was determined by comparison of the experimental and calculated electronic circular dichroism (ECD) spectra. A plausible biosynthetic pathway to 1 is proposed.

Rare and endangered plants have proven to be better sources for drug discovery than other botanic sources. Pinus dabeshanensis is an endangered plant listed in the China Plant Red Data Book, and has never been phytochemically investigated. In the present study, 11 new (dabeshanensins A–K, 1–11, resp.) and 28 related known naturally occurring diterpenoids were isolated from the shed trunk bark of this plant. The new structures were established by extensive spectroscopic methods and molecular modeling. Among them, dabeshanensin C (3) has an unprecedented bicyclo[3.3.1]nonane ring system (rings B and C) by oxidative cleavage of the C-6/C-7 bond followed by the formation of a new C–C bond between C-6 and C-12. The plausible biosynthetic pathway to 3 is briefly discussed. Dabeshanensins A (1) and J (10), 12-hydroxydehydroabietic acid (33), abieta-8,11,13,15-tetraen-18-oic acid (35), and 15-hydroxy-7-oxo-8,11,13-abietatrien-18-oic acid (37) showed significant inhibitory effects against the human protein tyrosine phosphatase 1B (PTP1B) enzyme, a key target for the treatment of type-II diabetes and obesity, with IC50 values ranging from 5.4 to 50.9 μM.

A highly convergent, stereocontrolled total synthesis of the architecturally complex marine sponge metabolite (-)-enigmazole A has been achieved. Highlights include an unprecedented late-stage large-fragment Petasis-Ferrier union/rearrangement, a multicomponent Type I Anion Relay Chemistry (ARC) tactic, and a dithiane-epoxide union in conjunction with an oxazole-directed stereoselective reduction.

An effective late-stage large-fragment union/rearrangement exploiting the Petasis–Ferrier protocol, in conjunction with multicomponent Type I Anion Relay Chemistry (ARC) to access advanced intermediates, permits completion of a convergent, stereocontrolled total synthesis of the architecturally complex phosphomacrolide (−)-enigmazole A (1).

Two new 2,4'-epoxy-8,5'-neolignans (1 and 2), together with five known 7,9';7',9-diepoxylignans (3-7), were isolated from an ethyl acetate soluble portion of a hepatoprotective water decoction of Penthorum chinese. Their structures and absolute configurations were elucidated by extensive spectroscopic analyses and electronic circular dichroism (ECD) calculations. This is the second report of 2,4'-epoxy-8,5'-neolignans from plants. Compounds 2, 6, and 7 showed in vitro protective activities against acetaminophen-induced hepatocyte injury at 5 μM.

Seven lycopodine-type (annotinolide F and lycoannotines A–F), two lycodine-type (lycoannotines G and H), and one fawcettimine-type (lycoannotine I) previously undescribed naturally occurring Lycopodium alkaloids together with thirteen known ones were isolated from the whole plant of Lycopodium annotinum. Their structures and absolute configurations were determined by extensive spectroscopic methods, single-crystal X-ray diffraction, chemical transformation, and electronic circular dichroism (ECD) calculations. Among the isolates, annotinolide F, lycoannotines A and B are unusual 7,8-seco-lycopodane derivatives, and annotinolide F even further possesses a rare 8,5-lactone framework through a lactonization after the C-7/C-8 bond cleavage. Lycoannotine C is an uncommon 8,15-seco lycopodine-type alkaloid, whereas lycoannotine I represents the first example of a naturally occurring C-9/N bond cleavage product of fawcettimine-type alkaloid. Among them, only lycoannotine I was found to show considerable anti-butyrylcholinesterase (anti-BuChE) activity.