A Comparison of Three Different Biodegradable Aliphatic Oligoesters (PGA,PLLA, and PCL) with Similar Linear Alkyl End Groups by DSC and SAXS

The biodegradable aliphatic oligoesters polyglycolide (PGA), poly(L-lactide) (PLLA), and poly(?-caprolactone) (PCL) with similar number-average molecular weight M_n values but different linear alkyl end groups [CH₃?[CH₂?CH₂]_m?CH₂?] were compared in terms of their physical properties, parameters such as melting temperature (T_m), crystallinity (x_i), long period (L), and lamella thickness (D). They were analyzed by DSC and SAXS. The effect of a longer and nonpolar alkyl end group such as docosyl [CH₃?[CH₂?CH₂]₁₀?CH₂?] on the long period (L) was more evident for PCL because it was the most nonpolar species in the family of oligoesters analyzed.     

Cooperative Bond Activation and Catalytic Reduction of Carbon Dioxide at a Group 13 Metal Center

A single‐component ambiphilic system capable of the cooperative activation of protic, hydridic and apolar H? X bonds across a Group 13 metal/activated β‐diketiminato (Nacnac) ligand framework is reported. The hydride complex derived from the activation of H₂ is shown to be a competent catalyst for the highly selective reduction of CO₂ to a methanol derivative. To our knowledge, this process represents the first example of a reduction process of this type catalyzed by a molecular gallium complex.     

A General and Scalable Synthesis of Aeruginosin Marine Natural Products Based on Two Strategic C(sp3)H Activation Reactions

An efficient and scalable access to the aeruginosin family of marine natural products, which exhibit potent inhibitory activity against serine proteases, is reported. This synthesis was enabled by the strategic use of two different, recently implemented C(sp³)? H activation reactions. The first method led to the common 2‐carboxy‐6‐hydroxyoctahydroindole (Choi) core of the target molecules on a large scale, whereas the second one provided rapid and divergent access to the various hydroxyphenyllactic (Hpla) subunits. This strategy allowed the synthesis of the aeruginosins 98B and 298A, with the latter being obtained in unprecedentedly large quantities.     

Isolation and Total Synthesis of Kirkamide,an Aminocyclitol from an Obligate Leaf Nodule Symbiont

The new C₇N aminocyclitol kirkamide ( 1 ) was isolated from leaf nodules of the plant Psychotria kirkii by using a genome‐driven ¹H NMR‐guided fractionation approach. The structure and absolute configuration were elucidated by HRMS, NMR, and single‐crystal X‐ray crystallography. An enantioselective total synthesis was developed, which delivered kirkamide ( 1 ) on a gram scale in 11 steps and features a Ferrier carbocyclization and a Pd‐mediated hydroxymethylation. We propose that kirkamide is synthesized by Candidatus Burkholderia kirkii, the obligate leaf symbiont of Psychotria kirkii. Kirkamide ( 1 ) was shown to be toxic to aquatic arthropods and insects, thus suggesting that bacterial secondary metabolites play a protective role in the Psychotria/Burkholderia leaf nodule symbiosis.     

Phenylalanine‐Derived Imidazolines Bearing Heteroaromatic Pendants: Synthesis,Characterization, and Application in the Asymmetric Henry Reaction

Starting from L ‐phenylalanine, (2S)‐3‐phenylpropane‐1,2‐diamine has been prepared and used as building block for the construction of the imidazoline ring. Four new optically pure NH‐imidazolines bearing different six‐membered heteroaromatic substituents on the C(2) position have been prepared and subsequently N‐modified. N‐Substitution afforded two regioisomers that were separated. Some of them proved to be instable and hydrolyzed to diamides. The molecular structures of NH‐imidazolines, both N‐substituted regioisomers, as well as diamides, were unambiguously confirmed by X‐ray‐analysis and NMR spectra. The successfully prepared imidazolines, as well as diamides, were applied as catalysts in a Cu(II)‐catalyzed Henry reaction achieving 26–98% chemical yields and enantiomeric excesses of 3–42%.     

Synthesis of Potentially Biologically Active 6‐(1,3‐Butadiynyl)purines

1,3‐Alkadiynyl(trimethyl)silanes were prepared by the Negishi or Sonogashira reactions of bromoethynyl(trimethyl)silane with several terminal alkynes in 34–75% yield. However, the direct Hiyama coupling of these compounds with 6‐iodopurine derivatives has not been successful. Therefore, a modified Sonogashira reaction using TBAF or CsF for in situ removal of the trimethylsilyl group has been utilized. This methodology afforded the desired 6‐(1,3‐butadiynyl)purines in 47–87% yield.