Theoretical Design of High-spin Organic Molecules with —^＊N—S— as a Spin-containing Fragment and Heterocycle as End Groups

IntroductionDesigns and syntheses of organic molecules withvery high-spin ground states have been a topic of greatinterest[1—8].One of the rational approaches to desig-ning high-spin molecules,which has been proposedand studied by several groups[9,10],in…     

Rhodium-catalyzed carbonylation of 2-alkynylbenzylamine: a new route to the synthesis of benzazepinones

Rhodium-catalyzed carbonylation of 2-alkynylbenzylamines under water-gas shift reaction conditions gives a seven-membered heterocyclic product, 2,4-disubstituted-1,4-dihydrobenz[c]azepin-3-ones, in a good yield.     

Synthesis of 5-heteroarylazulenes: first selective electrophilic substitution at the 5-position of azulene

1,3-Di-tert-butylazulene reacted with highly electrophilic trifluoromethanesulfonate of N-containing heterocycles to give 5-(dihydroheteroaryl)azulene derivatives in good yield and treatment of the 5-(dihydroheteroaryl)azulene derivatives with KOH afforded 5-(heteroaryl)azulenes in excellent yield.     

Mechanism of the cyclization of dimethyl diethynyl silane with selenium tetrabromide: Computational and structural studies, and monitoring

The structure of 2,4-dibromo-2-dibromomethyl-3,3-dimethyl-1-selena-3-silacyclopentene-4, formed by regioselective electrophilic addition of SeBr₄ to dimethyl diethynyl silane, has been determined using X-ray analysis technique. Quantum chemistry methods were used to study elementary stages of the reaction. It was found that the first stage consisted of SeBr₄ conversion into bimolecular complex Br₂?SeBr₂, initiated by dimethyl diethynyl silane. Possible formation of five-membered and six-membered heterocycles involves different cyclization mechanisms. The formation of only five-membered heterocycle is explained by kinetically preferable ring closure through four-center transition state. The conclusions obtained by calculations were confirmed by monitoring of the reaction using ¹H NMR method.     

含有杂环基侧链的新型聚硅氧烷

含有功能性基团的聚硅氧烷的研究一直是有机硅化学中十分活跃的研究领域之一。当含N、S等杂环引入聚硅氧烷链中后，由于杂环基的生理活性、催化活性及光电特性，因而含不同杂环基团的聚硅氧烷（POS）可分别用作催化剂、光电材料、医学材料等。当用作药物载体时，可提高药物的利用率和靶向性，也可降低某些药物的毒性。含环糊精侧基、冠醚侧基的POS亦可应用于气相色谱固定相、相转移催化剂。本文对近年来有关侧链含有吡啶、咪唑等杂环及环糊精基团等功能性侧基的聚硅氧烷结构、合成、及应用作一详细的评述并进行了展望。     

Synthesis of fused bicyclic pyridines with microwave-assisted intramolecular hetero-Diels-Alder cycloaddition of acetylenic pyrimidines

A series of acetylenic pyrimidines was synthesized and subjected to microwave irradiation. In contrast to conventional heating, the microwave irradiations generally gave clean conversion to fused bicyclic pyridines for all substrates reported with shorter reaction time. This method has been successfully applied to the synthesis of both fused lactones and lactams.     

Diversity-generation from an allenoate-enone coupling: syntheses of azepines and pyrimidones from common precursors

Amine-catalyzed coupling reactions of allenoate esters and α,β-unsaturated carbonyls lead to a diverse range of α,α′-disubstituted allenoates. With appropriately substituted monomers, intermolecular reactions can lead to pyrimidone products. Alternatively, with amine substituted allenoates, a 7-endo-dig cyclization can be carried out such that a divergent pathway is observed that leads to azepine scaffolds.     

CRYSTAL AND MOLECULAR STRUCTURE OF 4-CHLORO-5- ETHYL-5-METHYL-3-PHENYL-1, 3, 4-DIAZAPHOSPHOLIDIN-2-THIONE-4-SULFIDE

<正> Crystal of the title compound Mr=304. 80 belongs to the triclinic, space group P1, with a = 7. 282)2), b=9. 064(2), c=11. 737(5) A , α=75. 79 (3), β=78. 70(3), γ=88. 49(2)°, V-736. 21 A3, Z=2, Dx = l. 375 g/cm3. The final refinement is converged with R=0. 062 and Rw= 0. 069.The five-membered heterocycle is in envelope conformation. The P - N bond length (1. 68(1)) indicates that the dπ-Pπ bond between P and N of the title compound is stronger than that of the corresponding 4-phenyl compound.     

Multicomponent synthesis of epoxy-tetrahydronaphthyridine and structural diversification by subsequent fragmentation

Three-component reaction of an α-isocyanoacetamide 7, an homoallylamine 8 and an aldehyde 9 in methanol at room temperature provides oxa-bridged tricycle 4 in good to excellent yield as a mixture of two separable diastereoisomers. In this one-pot multicomponent process, one C-N, one C-O and three C-C bonds are formed with concomitant creation of five asymmetric centers and three rings. Fragmentation of epoxy-tetrahydronaphthyridine 4 affords differentially substituted 5,6,7,8-tetrahydro-1,7-naphthyridine (5, 6) depending on the reaction conditions, providing thus additional structural diversity. A one-pot three-component synthesis of 5,6,7,8-tetrahydro-1,7-naphthyridine (6) from 7, 8 and 9 is also documented.     

Synthesis of 5-(7-Hydroxyheptyl)-1,2-dithiolan-3-one 1-Oxide,a Core Functionality of Antibiotic Leinamycin

5-(7-Hydroxyheptyl)-1,2-dithiolan-3-one 1-oxide was designed and synthesized in our laboratories that contain the heterocycle of 1,2-dithiolan-3-one 1-oxide, a reactive core of antibiotic leinamycin. In addition, the activated ester of 5-(7-hydroxyheptyl)-1,2-dithiolan-3-one 1-oxide was prepared, which presumably is useful for coupling this DNA-cleaving functionality to certain DNA-binding agents.