Search

One new spirocyclic lactone, terreinlactone C (1), and one new benzopyran derivative, 2,2-dimethyl-3-hydroxychroman-6-aldehyde (2), were discovered from the fungus Aspergillus terreus. The chemical structures of compounds 1 and 2 were elucidated by detailedly analyzing NMR and HRESIMS data. Compound 1 is the first natural product with a 1-oxaspiro[4.5]decan-2-one ring system and a possible biogenetic pathway is proposed. Two compounds were tested for their cytotoxic activities against five human cancer cell lines.[Formula: see text].

A highly regioselective approach to access amide enol carbamates and carbonates 5a-5c', 7a-7h, and 9 was developed through Cu(OTf)2-catalyzed reactions of ynamides 4 with t-butyl carbamates 2 and 8 and t-butyl carbonates 6. Moreover, this strategy was successfully applied to generate amide enol carbamates 11a-11s and 14a-14f from imides 10 and 13 with ynamides through an N-Boc cleavage-addition ring-opening process. A range of substituents was amenable to this transformation, and the desired amide enol carbamates and carbonates were obtained in moderate to good yields.

Recently, it was demonstrated in an inviscid flow that burst-and-coast or intermittent swimming can save energy when compared with continuous swimming and that the energy savings are maximized for ...

An efficient method for asymmetric synthesis of epohelmins A (3), B (4) and their isomer 24 is detailed in this report. The key feature in this divergent synthesis includes the SmI2-induced cross-coupling of N-tert-butanesulfinyl imine 10 with chiral aldehyde 9 derived from d -malic acid. A cascade cyclization to the pyrrolizidine skeleton is achieved in our synthetic route for epohelmins. In addition, an interesting intramolecular oxa-Michael addition was observed for epohelmin A (3).

A convenient method for diastereoselective synthesis of the key intermediate 5 from triheterocyclic fragment and polyketide 6 for hoiamides A (1) and B (2) was developed. The main feature is the successive construction of four stereogenic centers from C33 to C36 for hoiamides A (1) through the well-established Oppolzer’s anti-aldol and Paterson’s anti-aldol methodology. Furthermore, asymmetric allylation was also utilized as a key step to form the stereogenic center at C32 for hoiamides A (1).

An efficient asymmetric approach to access functionalized pyrido- and pyrrolo[1,2- c][1,3]oxazin-1-ones has been developed through a nucleophilic addition-cyclization process of N, O-acetal with ynamides. A number of substituted ynamides 8a-8o and 3-silyloxypyrrolidine or piperidine N, O-acetals 6a, 7 were amenable to this transformation, and the desired products 9a-9o, 10a-10m were obtained with excellent regioselectivities and outstanding diastereoselectivities. Moreover, chiral ynamides 14a-14f could also experience this addition-cyclization process to afford products 15a-15f in excellent yields.

High performance mordenite membranes were successfully prepared in a short synthesis time from fluoride-containing dilute solution without organic template under microwave-assisted heating. The effects of crystallization temperature, fluoride ion and aluminum source on the membrane morphology and separation performance for dehydration of acetic acid by pervaporation were systematically investigated. High performance mordenite membranes with a thickness about 5 µm could be prepared from dilute solution with composition of SiO 2 : 0.06Al 2 O 3 :0.24Na 2 O:0.3NaF:120H 2 O at 165 °C for 4 h using various aluminum sources. These mordenite membranes exhibited high fluxes of 0.87±0.06 kg m −2 h −1 and excellent selectivities, that is only pure water was detected in the permeate side for dehydration of 90 wt% acetic acid aqueous mixtures at 75 °C. The reproducibility of mordenite membranes was high, using the fluoride-containing dilute solution under microwave-assisted heating, which forebodes a promising prospect for industrial applications in preferential separation of water from acetic acid aqueous solutions.

Three-dimensional beehive-like hierarchical porous carbons (HPCs) have been prepared by a facile carbonization of polymethylmethacrylate (PMMA)/polyacrylonitrile (PAN) core-shell polymer particle followed by KOH activation. The all-organic porogenic core-shell precursor was synthesized by a simple and green surfactant-free emulsion polymerization. The as-obtained HPCs show favorable features for electrochemical energy storage such as high specific surface area of up to 2085 m 2 g −1 , high volume of pores up to 1.89 cm 3 g −1 , hierarchical porosity consisting of micro, meso, and macropores, turbostratic carbon structure, uniform pore size and rich oxygen-doping (21.20%). The supercapacitor performance of HPCs exhibit a high specific capacitance 314 F g −1 at a current density of 0.5 A g −1 and 237 F g −1 at a current density of 20 A g −1 , ultra-high rate capability with 83% retention rate from 1 to 20 A g −1 and outstanding cycling stability with 96% capacitance retention after 2000 cycles. The facile, efficient and green synthesis strategy for novel HPCs from polymer sources could find use in supercapacitors, lithium ion batteries, fuel cells and sorbents.

An efficient approach for asymmetric synthesis of (+)-spicigerine, (+)-cassine and their 3-epimers has been developed through the intramolecular diastereoselective tandem addition/cyclisation process of α-chiral aldimine 9 with methylmagnesium bromide and the asymmetric addition of nucleophilic reagents to aminal 14. Moreover, the first asymmetric synthesis of (+)-spicigerine has been achieved in this manuscript. In this synthetic strategy, the asymmetric syntheses of (+)-spicigerine and (+)-cassine was achieved in a 14% overall yield and nine steps and an 18% overall yield and seven steps from cheap α-chiral aldimine 9, respectively.

A diastereoselective new approach for the synthesis of trans-4-hydroxy-5-allyl-2-pyrrolidinone 9 has been developed through In-mediated allylation of α-chiral aldimine 8 with allyl bromide. The stereochemistry at the C-2 stereogenic center of 9 was controlled by both the α-OTBS substitution and the sulfinamide moiety. The utility of this asymmetric allylation is demonstrated by the asymmetric syntheses of epohelmins A (4) and B (10).

An efficient and step-economical approach to access functionalized pyrrolizidine derivatives by a one-pot tandem sequence, including an aldol condensation and subsequent 1,3-dipolar cycloaddition process, has been developed, starting from acetone, aldehyde, and proline. A number of substituted aromatic aldehydes were amenable to this transformation, and the desired products, racemic 7a–7w and chiral 9a–9m, were obtained with excellent regioselectivities and outstanding diastereoselectivities. Moreover, in situ NMR studies revealed MgSO4 could effectively promote the aldol condensation pathway in this tandem process.

In this report, the originally proposed rupestonic acid (5) and pechueloic acid (3) were efficiently synthesized. The chiral lactone 13, recycled from the degradation of saponin glycosides, was utilized to prepare the key chiral fragment 11. During the exploration of this convergent assembly strategy, the ring-closing metathesis (RCM), SmI2-prompted intermolecular addition, and [2,3]-Wittig rearrangement proved to be effective transformations for the synthesis of subunits.