RESUMO
An axial chiral tetrachlorinated bisbenzo[a]phenazine has been discovered that undergoes an alkane-induced shift in the solid state from a disordered amorphous form to an ordered polycrystalline form. This phase transition is caused by the formation of pores that accommodate linear alkanes of varying lengths with a very strong affinity as judged by differential scanning calorimetry. Single crystal X-ray structure analysis revealed that a series of weak phenolic OH···Cl hydrogen bonds dictates the pore structure. These weak interactions can be disrupted mechanically, causing the material to revert to the amorphous form. Notably, the interchange between the amorphous and crystalline forms is readily reversible and is easily observed by characteristic colorimetric changes. Measurements via photoimage processing reveal that the degree of color change is dictated by the type of alkane employed.
Assuntos
Alcanos/química , Fenazinas/química , Cloro/química , Cristalografia por Raios X , Halogenação , Ligação de Hidrogênio , Modelos Moleculares , Transição de FaseRESUMO
The development of the first asymmetric synthesis of a chiral anthraquinone dimer is outlined, resulting in the first total synthesis of (S)-bisoranjidiol. Rather than a biomimetic dimerization retrosynthetic disconnection, the anthracenyl ring systems are generated after formation of the axially chiral binaphthalene framework. This synthetic strategy has enabled the synthesis of several analogues. Key features of the synthesis include the enantioselective coupling of a hindered 2-naphthol containing substitution peri to the site of C-C bond formation, the regioselective oxidation of 8,8'-hydroxylated binaphthols to binaphtho-para-quinones, and a tandem regioselective Diels-Alder/aromatization reaction.
Assuntos
Antraquinonas/química , Antraquinonas/síntese química , Produtos Biológicos/química , Produtos Biológicos/síntese química , Quinonas/química , Catálise , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Oxirredução , EstereoisomerismoRESUMO
The selective oxidation of a series of functionalized 8,8'-hydroxylated binaphthols to binaphtho-para- and binaphtho-ortho-quinones has been realized using either a Co-salen catalyst or ortho-iodoxybenzoic acid. A unique spirocyclic bis-spironaphthalenone was also obtained in good yield via a phenyliodonium diacetate promoted oxidative dearomatization.
Assuntos
Naftóis/química , Quinonas/síntese química , Compostos de Espiro/síntese química , Catálise , Etilenodiaminas/química , Estrutura Molecular , Oxirredução , Quinonas/química , Compostos de Espiro/química , EstereoisomerismoRESUMO
The structure of a reported natural product isolate has been revised from (S)-2,2'-dimethoxy-[1,1'-binaphthalene]-5,5',6,6'-tetraol to a known tetrabrominated diphenyl ether. After total synthesis of the reported binaphthalenetetrol was accomplished via a key reduction of a binaphtho-ortho-quinone, comparison of the physical properties and NMR spectroscopic data of the synthetic material indicated that the structure of the natural product isolate was incorrect. Evaluation of the authentic natural product suggested the structure is a tetrabrominated diphenyl ether, likely 3,5-dibromo-2-(3,5-dibromo-2-methoxyphenoxy)phenol.
Assuntos
Produtos Biológicos/química , Éteres Difenil Halogenados/química , Cristalografia por Raios X , Biologia Marinha , Conformação Molecular , Estrutura Molecular , Ressonância Magnética Nuclear Biomolecular , EstereoisomerismoRESUMO
The first enantioselective total synthesis of the bisanthraquinone (S)-bisoranjidiol and an unnatural regioisomer has been accomplished. Key features of the synthesis include the asymmetric oxidative biaryl coupling of a hindered 8-substituted 2-naphthol, selective para-quinone formation, and regioselective tandem Diels-Alder/aromatization reactions.