Enantioselective Total Synthesis of 3β‐Hydroxy‐7β‐kemp‐8(9)‐en‐6‐one,a Diterpene Isolated from Higher Termites

The first total synthesis of the title diterpene was accomplished starting from the Wieland–Miescher ketone. A diastereoselective sulfa‐Michael addition enabled the generation of the delicate β,γ‐unsaturated ketone moiety, while the tetracyclic kempane skeleton was readily constructed through domino metathesis.     

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Es wird über eine spezifische Abtrennung des Urans aus Mischungen radioaktiver Spaltprodukte mittels Dünnschichtchromatographie berichtet. Die bei kurz bestrahlten Uranproben am Uranfleck gefundene Radioaktivität kann auf Grund γ-spektrometrischer Messungen dem ²³⁹Np zugeordnet werden.     

Synthesis of (+)-boronolide and (+)-deacetylboronolide using Pd-catalyzed carbonylation and lactonization

(+)-Boronolide and (+)-deacetylboronolide were synthesized using Pd-catalyzed CO insertion and lactonization as the key step. As to the ¹³C NMR data of (+)-deacetylboronolide, the assignment at C-6 position should be revised.     

Recyclable MoO3 nanobelts for photocatalytic degradation of Rhodamine B by near infrared irradiation

Molybdenum trioxide (MoO₃) represented an excellent photocatalytic performance with many applications, including degradation of organic contaminants and splitting of water. This paper presented a new route to synthesize MoO₃ nanobelts with high aspect ratios and crystallinity by a hydrothermal technique. This work showed that the as-synthesized nanobelts exhibited strong photocatalytic activity to degrade an organic dye of Rhodamine B (RhB) in aqueous solution under the exposure of the light source in the near infrared wavelength range, significantly improving the photocatalytic activity of the nanobelts. The results also showed that for a small concentration of RhB at 7.5 mg/L a complete photodegradation (for a given MoO₃ nanobelts quantity of 0.1 g) can be reached after exposing for 60 min. For all concentrations of the RhB solution, the photodegradation exhibited an exponential dependence on the exposure time followed by a sudden shutdown, but no complete photodegradation can be reached. Also, the residual quantity of RhB in solution after the photocatalytic reaction was determined by the initial RhB concentration. The photocatalytic degradation can be interpreted by the pseudo–first-order equation for the absorption of liquid/solid based on solid capacity; thus, photocatalytic degradation can be attributed to the interaction between the photoexcited electrons in the substrate and the antibonding orbital of the RhB in solution. The sudden shutdown was due to the inability of the photoexcited electrons in the substrate hopping to the antibonding orbital of RhB in the presence of the RhB intermediate products from the degraded RhB. In addition, this work showed that the photocatalytic reaction can be recovered after a thermal treatment of postreacted MoO₃ nanobelts, enhancing the utilization efficiency of the catalysis.     

Divergent Synthesis of Bioactive Dithiodiketopiperazine Natural Products Based on a Double C(sp3)−H Activation Strategy

This article provides a detailed report of our efforts to synthesize the dithiodiketopiperazine (DTP) natural products (−)-epicoccin G and (−)-rostratin A using a double C(sp³)−H activation strategy. The strategy's viability was first established on a model system lacking the C8/C8’ alcohols. Then, an efficient stereoselective route including an organocatalytic epoxidation was secured to access a key bis-triflate substrate. This bis-triflate served as the functional handles for the key transformation of the synthesis: a double C(sp³)−H activation. The successful double activation opened access to a common intermediate for both natural products in high overall yield and on a multigram scale. After several unsuccessful attempts, this intermediate was efficiently converted to (−)-epicoccin G and to the more challenging (−)-rostratin A via suitable oxidation/reduction and protecting group sequences, and via a final sulfuration that occurred in good yield and high diastereoselectivity. These efforts culminated in the synthesis of (−)-epicoccin G and (−)-rostratin A in high overall yields (19.6 % over 14 steps and 12.7 % over 17 steps, respectively), with the latter being obtained on a 500 mg scale. Toxicity assessments of these natural products and several analogues (including the newly synthesized epicoccin K) in the leukemia cell line K562 confirmed the importance of the disulfide bridge for activity and identified dianhydrorostratin A as a 20x more potent analogue.     

Total Synthesis of Lajollamycin B

The first total synthesis of lajollamycin B, a structurally novel nitro-tetraene spiro-β-lactone/γ-lactone antibiotic, is described. The convergent synthesis involves the construction of the C8′–C11′ nitrodienylstannane and its coupling with the segment prepared from the C1′–C7′ ω-iodoheptadienoic acid and the right-hand heterocyclic fragment, which has been utilized for our previous syntheses of oxazolomycin A. The revision of the geometry of the terminal Δ^{10′, 11′}-double bond from E to Z is also described for the structure of natural lajollamycin B.