Decane Core Research Articles

Filicinic Acid-Based Meroterpenoids with Antiproliferative Activity against Prostate Cancer PC-3 Cells from Dryopteris wallichiana.

Nine new structurally diverse filicinic acid-based meroterpenoids (1-9) with four kinds of carbon skeletons were isolated from the rhizomes of Dryopteris wallichiana. Their structures, including the absolute configurations, were elucidated by comprehensive analysis of spectroscopic data, quantum chemical calculations, and single-crystal X-ray diffraction. Structurally, compounds 1-4 feature an unprecedented 6/6/5/6/6/6 hexacyclic system with a rare oxaspiro[4.5]decane core linking the filicinic acid and ent-kaurane-type diterpene moieties. Compounds 5-6 are rare hybrids of filicinic acid and carotane-type sesquiterpene. Compound 7 is an unusual rearranged filicinic acid-carotane-type sesquiterpene meroterpenoid. Compounds 8-9 are two enantiomeric pairs of new meroterpenoids constructed by filicinic acid and a germarane-type sesquiterpene. A plausible biosynthetic pathway for the nine compounds was proposed. Notably, compounds 5, 6, (+)/(-)-8, and (+)/(-)-9 were discovered to possess antiproliferative activity against PC-3 cells based on virtual screening, and in vitro bioassay. An interactive preprint version of the article can be found at https://www.authorea.com/doi/full/10.22541/au.172666991.17272585/v1.

Pogocablenes A-O, fifteen undescribed sesquiterpenoids with structural diversity from Pogostemon cablin

Fifteen previously undescribed sesquiterpenoids (pogocablenes A-O), three first discovered natural patchoulol-type ones, coupled with fourteen known ones, were isolated from the aerial parts of Pogostemon cablin. Among them, pogocablenes A and B, a pair of C2 epimers, possessed an unusual carbon skeleton with bicyclo[4.3.1]decane core. Pogocablene C, originated from eudesmane-type sesquiterpenoid, had an unprecedented bicyclo[5.4.0]undecane scaffold with a peroxy hemiactetal moiety. Pogocablene D possessed a rare tricyclo[5.2.2.01,5]undecane carbon skeleton derived from guaiane-type sesquiterpenoid. Pogocablene E was a 4,5-seco-guaiane derivative owning a peroxy hemiactetal unit and a spirocyclic skeleton. Pogocablene M was a nor-patchoulol-type sesquiterpenoid with α,β-unsaturated ketone moiety. Their structures with absolute configuration were determined by extensive spectroscopic analysis, in combination with quantum chemical calculation. In addition, the plausible biogenetic pathways of pogocablenes A-E were proposed. Furthermore, all isolates were evaluated for anti-influenza virus and anti-inflammatory effects.

Intramolecular Dearomative Inverse-Electron-Demand Diels Alder Strategy for the Total Synthesis of (+)-Alstonlarsine A.

An evolution of a synthetic route leading to a successful enantioselective total synthesis of monoterpenoid indole alkaloid (+)-alstonlarsine A is represented. The unique 9-azatricyclo[4.3.1.03,8]decane core was assembled through an efficient domino sequence comprising enamine formation in situ, followed by intramolecular dearomative inverse-electron-demand Diels Alder reaction. The preparation of the tricyclic dihydrocyclohepta[b]indole key intermediate via the intramolecular Horner-Wadsworth-Emmons reaction required a development of a new general method for the introduction of the phosphonoacetate moiety into the indole C-2 position, through copper-carbenoid insertion. The modular nature of the represented synthetic approach makes it suitable for the synthesis of analogues with different substituents' patterns.

Isolation and antihyperglycemic effects of garcibractinols A–H, intricate polycyclic polyprenylated acylphloroglucinols from the fruits of Garcinia bracteata

Eight previously undescribed polycyclic polyprenylated acylphloroglucinols (PPAPs) were isolated from the fruits of Garcinia bracteata and named garcibractinols A–H. Garcibractinols A–F (compounds 1–6) were bicyclic polyprenylated acylphloroglucinols (BPAPs) sharing a rare bicyclo[4.3.1]decane core. On the other hand, garcibractinols G and H (compounds 7 and 8) shared an unprecedented BPAP skeleton bearing a 9-oxabicyclo[6.2.1]undecane core. The structures andabsolute configurations of compounds 1–8 were determined by spectroscopic analysis,single-crystal X-ray diffraction analysis, and quantum chemical calculation. The breakage of the C-3/C-4 linkage through the retro-Claisen reaction was a key step in the biosynthesis of compounds 7 and 8. The antihyperglycemic effects of the eight compounds were evaluated in insulin-resistant HepG2 cells. At a concentration of 10 μM, compounds 2 and 5–8 significantly increased the glucose consumption in the HepG2 cells. Furthermore, compound 7 was more effective than metformin (which was used as a positive control) in promoting glucose consumption in the cells. The findings of this study suggest that compounds 2 and 5–8 have anti-diabetic effects.

Heimionones A-E, New Sesquiterpenoids Produced by Heimiomyces sp., a Basidiomycete Collected in Africa.

With heimionones A-E (1-5), five new terpenoids were isolated from submerged cultures of Heimiomyces sp. in addition to the previously described compounds hispidin, hypholomin B, and heimiomycins A and B. Planar structures of the metabolites were elucidated by 1D and 2D NMR in addition to HRESIMS data. While ROESY data assigned relative configurations, absolute configurations were determined by the synthesis of MTPA esters of 1, 3, and 5. The [6.3.0] undecane core structure of compounds 3-5 is of the asteriscane-type, however, the scaffold of 1 and 2 with their bicyclo [5.3.0] decane core and germinal methyl substitution is, to our knowledge, unprecedented. Together with several new compounds that were previously isolated from solid cultures of this strain, Heimiomyces sp. showed an exceptionally high chemical diversity of its secondary metabolite profile.

Euphylonoids A and B, Two Highly Modified Jatrophane Diterpenoids with Potent Lipid-Lowering Activity from Euphorbia hylonoma.

Euphylonoids A (1) and B (2), two highly modified jatrophane diterpenoids, were isolated from Euphorbia hylonoma. 1 represents a new 9(10→18)-abeo-8,12-cyclojatrophane skeleton containing a cage-like 3,8-dioxatricyclo[5.1.2.04,9]decane core, while 2 is a 14(13→20)-abeo-8,12-cyclojatrophane featuring an unusual 17-oxatetracyclo[12.2.1.01,5.09,13]heptadecane framework. Their structural elucidation was completed by spectroscopic, chemical, computational, and single-crystal X-ray diffraction means. 2 significantly inhibited early adipogenesis in 3T3-L1 adipocytes via activating AMP-activated protein kinase signaling.

Supercooling elimination of cryogenic-temperature microencapsulated phase change materials (MPCMs) and the rheological behaviors of their suspension

Phase change materials (PCMs) when amalgamated in a shell material to form microencapsulated-PCMs (MPCMs) usually exhibit high levels of supercooling due to the limited crystallization process. In the present study, various efforts were made to reduce this phenomenon, including increasing the MPCM size, employing nucleating agents, and embedding copper nanoparticles into the MPCM shells. It was observed that with an increase in the microcapsule size from 43 μm to 76 μm, the supercooling was reduced by a value of 10.2 °C from melting/freeing point peak temperature differences of 37.6 to 27.4 for the 1200 rpm and 800 rpm samples respectively. Comparatively, the implementation of octadecanol nucleating agent 30 wt % resulted in a reduction of supercooling by 22.9 °C. The introduction of Cu nanoparticles with a decane core can also reduce the supercooling degree by 4.6 °C, while the thermal conductivity the MPCM samples with a hexadecane core increased from 0.173 to 0.182 W m−1 K−1 before and after the addiction of the Cu nanoparticles. Furthermore, di(propylene glycol) methyl ether was used as a carrier fluid for the MPCMs to study the slurry rheological behaviors with various MPCM compositions. It was observed that the MPCM suspension with 10–20% MPCM mass concentration did not exhibit shear thinning, while the 30% sample conveyed shear thinning properties. Furthermore, near the crystallization temperature of the PCM, the slurry viscosity sharply rose, attributed to the volume changes and non-cooperative motion of MPCM microcapsules.

Total Syntheses of Chloropupukeananin and Its Related Natural Products

Chloropupukeananin is a natural product that inhibits HIV-1 replication and has antitumor activity. Its structure consists of a chlorinated tricyclo[4.3.1.03,7]decane core skeleton with an array of highly oxidized multifunctional groups. In the biosynthesis of chloropupukeananin, (+)-iso-A82775C and (−)-maldoxin are employed as biosynthetic precursors for the intermolecular Diels–Alder and carbonyl–ene reactions, followed by the migration of the p-orcellinate group. Chloropupukeanolides and chloropestolides are intermediates and isomers in biosynthesis; their unique chemical structures and biosynthetic pathways have attracted significant attention from synthetic chemists. In this review, I present the synthetic studies on chloropupukeananin and its related compounds that have been conducted thus far.

Total Synthesis of (+)-Alstonlarsine A.

An enantioselective total synthesis of (+)-alstonlarsine A (1), a monoterpenoid indole alkaloid possessing a unique pentacyclic skeleton as well as a rare biological activity, is achieved. The key step is an efficient domino sequence, comprising enamine formation followed by an inverse-electron-demand intramolecular dearomative Diels-Alder cycloaddition for the construction of 9-azatricyclo[4.3.1.03,8 ]decane core. The key intermediate for this domino sequence was synthesized by a newly developed methodology, relying on indole C(2) -H bond functionalization, combined with intramolecular Horner-Wadsworth-Emmons reaction. This tactical combination offers a new general entry into other (privileged) tricyclic frameworks possessing indole ring fused to 6-, 7- or 8-membered rings.

Total Synthesis of (+)‐Alstonlarsine A

An enantioselective total synthesis of (+)-alstonlarsine A (1), a monoterpenoid indole alkaloid possessing a unique pentacyclic skeleton as well as a rare biological activity, is achieved. The key step is an efficient domino sequence, comprising enamine formation followed by an inverse-electron-demand intramolecular dearomative Diels–Alder cycloaddition for the construction of 9-azatricyclo[4.3.1.03,8]decane core. The key intermediate for this domino sequence was synthesized by a newly developed methodology, relying on indole C(2)-H bond functionalization, combined with intramolecular Horner–Wadsworth–Emmons reaction. This tactical combination offers a new general entry into other (privileged) tricyclic frameworks possessing indole ring fused to 6-, 7- or 8-membered rings.

Cytotoxic analogues of marine diterpenoid plumisclerin A by shifting the lipophilic branch on the characteristic tricyclic core.

Plumisclerin A is one of the most complex cytotoxic xenicane diterpenes from marine sources, featuring a unique congested and rigid tricyclo[4.3.1.01,5]decane core and a lipophilic acyl chain. This work explored a number of new analogues of plumisclerin A through modifying the characteristic tricyclo[4.3.1.01,5]decane core with lipophilic chains starting from a common lactone intermediate. Bioactivity examination of all the synthetic analogues shows that new analogues 2a, 18 and 21 exhibited comparable inhibitory potencies to that of the natural product against the proliferation of cancer cells. Structural comparison of these bioactive natural and unnatural compounds reveals that the location of lipophilic substituent(s) on the tricyclo[4.3.1.01,5]decane core is spatially flexible, and this work thus offers a new channel to diverse bioactive analogues of plumisclerin A.

Litosetoenins A-E, Diterpenoids from the Soft Coral Litophyton setoensis, Backbone-Rearranged through Divergent Cyclization Achieved by Epoxide Reactivity Inversion.

Litosetoenins A-E (1-5), five new ring-rearranged serrulatane-type diterpenoids with a common tricyclo[3.0.4]decane core, along with a known diterpenoid glycoside (6), a related known diterpenoid (7), and four known sesquiterpenoids (8-11), were isolated from a Balinese soft coral Litophyton setoensis. Spirolitosetoenin A (5a) and isospirolitosetoenin A (5b), featuring an unprecedented spiro[4,5]decane core, were obtained after treatment of compound 5 with HCl in methanol. The structures of new compounds were elucidated by extensive spectroscopic analysis, quantum mechanical nuclear magnetic resonance approach, and chemical methods. A plausible biosynthetic pathway involving an unusual divergent biogenesis was proposed.

New iridoid and phenylethanoid glycosides from the roots of Scrophularia ningpoensis

Two new iridoid glycosides, scrophularosides A and B (1–2), two phenylethanoid glycosides, scrophularosides C-D (3–4) and eight known compounds (5-12) were isolated from the roots of Scrophularia ningpoensis. Their structures were elucidated via the interpretation of spectroscopic methods, especially 2D NMR and mass analyses. Compound 1 was a novel iridoid glycoside which possessed a 5/6/7/6 ring system with an unprecedented trioxabicyclo [4.3.1] decane core. The anti-inflammatory potential of new compounds 1–4 was evaluated by determining their ability to inhibit lipopolysaccharide (LPS) induced NO production in RAW 264.7 macrophage cells.

Yanhusanines A–F, Isoquinoline-Derived Alkaloid Enantiomers from Corydalis yanhusuo and Their Biological Activity

Six new pairs of isoquinoline alkaloid enantiomers, designated as yanhusanines A-F (1-6), were isolated from an aqueous extract of Corydalis yanhusuo tubers. The structures of these enantiomers were elucidated via physicochemical analysis and a variety of spectroscopic methods. All compounds were resolved into their enantiomers via chiral-phase HPLC, and their configurations were determined by DP4+ NMR calculation methods, specific rotations, and comparison of experimental and calculated ECD spectra. Compounds 1-6 bear a rare 9-methyl moiety, and compound 1 possesses a rare 1-oxa-6-azaspiro[4.5]decane core containing an N-CHO group. Compounds (+)-2, (-)-2, (+)-4, (-)-4, (+)-5, (-)-5, (+)-6, and (-)-6 exhibited selective inhibitory activities against human carboxylesterase (hCE2), in the IC50 value range of 2.0-13.2 μM.

Six-Step Total Synthesis of (±)-Conolidine.

A concise total synthesis of (±)-conolidine, a potent nonopioid analgesic, in 19% overall yield is described here. A gold(I)-catalyzed Conia-ene reaction (Toste cyclization) and a Pictet-Spengler reaction served as key transformations for assembling the 1-azabicyclo[4.2.2]decane core and defining the geometry of the exocyclic double bond. The activation energies of formation of the vinyl-gold intermediates were calculated and revealed a silyl enol ether with an unprotected indole moiety as a suitable precursor for the Toste cyclization. This six-step synthesis did not involve any nonstrategic redox manipulations.

Asymmetric Synthesis of the DEFG Rings of Solanoeclepin A.

Starting from ( R)-seudenol, an asymmetric synthesis of the DEFG rings of solanoeclepin A has been developed. The key transformations include the substrate-controlled asymmetric Staudinger ketene cycloaddition and the intramolecular aldol reaction leading to the tricyclo[5.2.1.01,6]decane core of solanoeclepin A in 10 steps in the longest reaction sequence.

Physical modification of carbon nanotubes with a dendrimer bearing terminal mercaptoundecahydrododecaborates (Na2B12H11S)

AbstractThe thiol‐substituted B12‐cluster mercaptoundecahydro‐closo‐dodecaborate Na2[B12H11SH] (BSH) was successfully attached to a poly(amido)amine (PAMAM) dendrimer, which contains a bis(decyloxy)decane core. The physical modification of single‐walled carbon nanotubes (SWCNTs) with dendrimer(SB12)4 afforded a SWCNT/dendrimer(SB12)4 nanohybrid that exhibited NIR‐I‐to‐NIR‐II fluorescence. Herein, we describe a promising strategy for in vivo imaging of boron clusters that may be widely applicable to boron neutron capture therapy.

Mollebenzylanols A and B, Highly Modified and Functionalized Diterpenoids with a 9-Benzyl-8,10-dioxatricyclo[5.2.1.01,5]decane Core from Rhododendron molle.

Two highly modified and functionalized diterpenoids, mollebenzylanols A (1) and B (2), and a known grayanane diterpenoid rhodojaponin III (3) were isolated from Rhododendron molle. Their structures were determined by spectroscopic data analysis, an electronic circular dichroism (ECD) exciton chirality method, ECD calculations, and X-ray diffraction analysis of the p-bromobenzoate ester of 1 (1a). Compounds 1 and 2 possess an unprecedented diterpene carbon skeleton featuring a unique 9-benzyl-8,10-dioxatricyclo[5.2.1.01,5]decane core, and their plausible biosynthetic pathways are proposed. Their PTP1B inhibitory activity and modes of action were investigated.

Belamcandanes A and B, two unprecedented tricyclic-iridal triterpenoids from Belamcanda chinensis

Two unprecedented tricyclic-iridal triterpenoids, belamcandanes A–B (1–2), have been isolated from the rhizomes of Belamcanda chinensis. The structures of 1 and 2 were assigned by interpretation of spectroscopic data including NMR and MS, and their absolute configurations were assigned by ECD calculation. Compounds 1–2 possess a spiro[4,5]decane core structure and a α-terpineol moiety, representing the first example of tricyclic-iridal triterpenoids. The plausible biogenetic pathway for 1 and 2 is also proposed.

Synthesis of a poly(amidoamine) dendrimer having a 1,10-bis(decyloxy)decane core and its use in fabrication of carbon nanotube/calcium carbonate hybrids through biomimetic mineralization

A new dendritic dispersant of carbon nanotubes (CNTs) was synthesized and applied for the noncovalent functionalization of single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs). The 1,10-bis(decyloxy)decane core of the poly(amidoamine) dendrimer strongly adhered to the sidewalls of CNTs to form CNT/dendrimer supramolecular nanocomposites having many carboxyl groups (–COOH) on the surface. Then, crystallization of calcium carbonate (CaCO3) by the CO2 diffusion technique in aqueous environments using the CNT/dendrimer supramolecular nanocomposites as scaffolds afforded monodisperse spherical CNT/CaCO3 nanohybrids consisting of CNTs and calcite nanocrystals. The morphologies of the SWCNT/CaCO3 hybrids and MWCNT/CaCO3 hybrids were almost the same.