Reactions of 2,2-disubstituted 1,1-dicyanoethenes with β-dimethylaminoacrolein aminal and 3-dimethylamino-1,1,3-trimethoxypropane

A reaction of 2,2-disubstituted 1,1-dicyanoethenes with β-dimethylaminoacrolein aminal and 3-dimethylamino-1,1,3-trimethoxypropane leads to substituted 6,6-dicyano-1-dimethyl-aminohexatrienes and an organic salt containing 1,1,9,9-tetracyano-2,8-diphenylnona-2,4,6,8-tetraenide as the anion and (dimethylaminopropenylidene)dimethylammonium as the cation, on the basis of which new cation-anionic polymethine dyes were obtained. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1639–1643, August, 2008.     

Compensation effect in the electrical conduction process in a series of pyrenyl polyenes

The semiconductive properties of a series of pyrenyl polyenes of the type R-(CH=CH)_n-R, are studied as a function of the adsorption of different amount of a vapour. With regard to the compensation temperature (T ₀) the compounds are divided into two groups. For compounds which have odd number of double bonds,T ₀ is infinite and in compounds having even number double bonds,T ₀ is finite.T ₀ for II₂ is higher while that of II₄ is lower than the experimental temperature. DifferentT ₀ for the compounds having odd or even number of double bonds suggests a physical basis for the compensation rule, which we believe, is related to the molecular and crystalline structure of the compounds     

RuO4-promoted oxidative polycyclization of isoprenoid polyenes. A further insight into the stereochemistry of the process

Further studies on the RuO₄-catalyzed oxidative polycyclization of isoprenoid polyenes have been carried out. The configuration of the tris-THF product from the oxidation of geranylgeranyl acetate has been determined by a combination of spectral and chemical correlation methods. The oxidation of (E,Z)-farnesyl acetate, synthesized from nerol, has been carried out. This process stops at the first cyclization indicating that an E configuration of the Δ⁶ double bond is needed for the second cyclization to occur. The results are discussed in comparison with previous knowledge on the related Re(VII) polycyclization of polyenic bis-homoallylic alcohols.     

溶剂密度对β胡萝卜素拉曼散射截面的影响

测量了含有9个CC共轭双键的链状多烯类生物分子β胡萝卜素在9种溶剂中的紫外—可见吸收和拉曼光谱.结果表明,β胡萝卜素C—C,CC键拉曼散射截面随溶剂体密度增加而线性增加,其机理是β胡萝卜素分子在体密度大的溶剂中受浮动干扰小,分子结构有序性高,π电子离域扩展,产生强的相干弱阻尼CC键振动,而产生大的拉曼散射截面.密度对分子拉曼散射截面影响研究还没见过报道,本文为多烯类链状分子的光散射理论研究提供了实验线索,也对多烯类链状分子性能研究及光电器件研制有参考价值. 关键词： 拉曼散射截面 多烯分子 吸收光谱 分子结构有序     

Modeling red coral (Corallium rubrum) and African snail (Helixia aspersa) shell pigments: Raman spectroscopy versus DFT studies

Pigments from red coral (Corallium rubrum) and African snail (Helixia aspersa) shell were studied non‐invasively using Raman spectroscopy with 1064‐nm laser beam. The two observed bands because of organic pigments confined in biomineralized CaCO₃ matrix at about 1500 and 1100 cm⁻¹ were assigned to ν(CC) and ν(C―C), respectively. Both signals originate from polyene(s) of largely unknown structure, containing several conjugated CC bonds. The small peak at 1016 cm⁻¹ in the Raman spectrum of coral pigment was assigned to in‐plane ―CH₃ rocking or structural deformation of polyene chain because of spatial confinement in the mineral matrix. The organic pigments in red coral and snail shell were present in inorganic matrix containing aragonite (shell) and calcite (coral). In addition, using Raman spectroscopy, it was observed that aragonite was replaced by calcite as result of healing damaged parts of snail shell. This is an important finding which indicates a great potential of nondestructive Raman spectroscopy instead of X‐ray technique, as a diagnostic tool in environmental studies. To support analysis of the observed Raman spectra detailed calculations using density functional theory (DFT with B3LYP and BLYP density functionals) on structure and vibrations of model all‐trans polyenes were undertaken. DFT calculated CC and C―C stretching frequencies for all‐trans polyenes containing from 2 to 14 CC units were compared with the observed ν(CC) and ν(C―C) band positions of the studied coral and shell. Individual correction factors were used to better match theoretical wavenumbers with observed band positions in red coral and African snail. It was concluded that all‐trans polyene pigments of red coral and dark parts of African snail shell contain 11–12 and 14 CC double bond units, respectively. However, Raman spectroscopy cannot produce any clear information on the presence and nature of the end‐chain substituents in the studied pigments. Copyright © 2016 John Wiley & Sons, Ltd.     

Total Synthesis of Belizentrin Methyl Ester: Report on a Likely Conquest

The assigned structure of the dinoflagellate‐derived toxin belizentrin was prepared by total synthesis in form of the corresponding methyl ester for stability reasons. The successful route features an unusual solution for the preparation of a recalcitrant ylide on a C‐glycosidic segment; moreover, it involves an asymmetric hetero‐Diels–Alder reaction en route to the tertiary hemiacetal substructure, a Negishi cross‐coupling of two elaborate building blocks, and a macrocyclization based on an intramolecular aminolysis of a spirolactone. A modified Kocienski olefination ultimately allowed the polyol side chain to be attached to the macrocycle although this transformation faced the exceptional base sensitivity of this polyunsaturated target compound.     

Reconstitution of a Type II Polyketide Synthase that Catalyzes Polyene Formation

While type II polyketide synthases (PKSs) are known for producing aromatic compounds, a phylogenetically new subfamily of type II PKSs have been recently proposed to synthesize polyene structures. Here we report in vitro analysis of such a type II PKS, IgaPKS for ishigamide biosynthesis. The ketoreductase (Iga13) and dehydratase (Iga16) were shown to catalyze the reduction of a β‐keto group and dehydration of a β‐hydroxy group, respectively, to form a trans double bond. Incubation of the acyl carrier protein (Iga10), the ketosynthase/chain length factor complex (Iga11–Iga12), Iga13 and Iga16 with malonyl and hexanoyl‐CoAs and NADPH followed by KOH hydrolysis resulted in the formation of four unsaturated carboxylic acids (C₈, C₁₀, C₁₂, and C₁₄), indicating that IgaPKS catalyzes tetraene formation by repeating the cycle of condensation, keto‐reduction and dehydration with strict stereo‐specificity. We propose “highly reducing type II PKS subfamily” for the polyene‐producing type II PKSs.     

Isomer combinatorics for acyclic conjugated polyenes: enumeration and beyond

A combinatorial approach to fully conjugated acyclic polyenes (C _N H _{N +2}) is considered with a view to the extension of standard enumeration techniques to treat a widened range of chemically interesting features. As a first step, enumerations are made respecting: placement of single and double bonds, the occurrence of cis/trans isomers, and the degree (and type) of “radicality” of such conjugated networks. As a further extension, several structural (graph-theoretic) invariants averaged over various types of isomer classes and sub-classes are made, and then these invariants are utilized to estimate several physicochemical properties averaged over these same classes or sub-classes. The properties currently so considered are heats of formation, indices of refraction, and magnetic susceptibilities. Finally, the asymptotic behaviors of isomer counts and isomer properties in the many-atom limit is elaborated. Received: 10 August 1998 / Accepted: 17 November 1998 / Published online: 16 March 1999