Benzothiazines in synthesis. Formal synthesis of erogorgiaene

A benzothiazine, readily available in enantiomerically pure form via a completely selective, intramolecular addition of a sulfoximine-stabilized carbanion to an α,β-unsaturated ester, could be converted to a precursor to erogorgiaene in good overall yield.     

Asymmetric synthesis of cyclobutanones: synthesis of cyclobut-G

A simple, efficient, and stereoselective approach has been developed for obtaining chiral cis- and trans-disubstituted cyclobutanones from readily available alkyl- and functionalized alkyl-substituted enol ethers. The usefulness of these cyclobutanones is illustrated by an enantioselective synthesis of cyclobut-G (Lobucavir).     

金属蒸气合成在金属有机合成中的应用

本文简要地介绍了金属蒸气合成法的基本原理、仪器和实验技术, 并按金属原子分别与炔、单烯、多烯、环烯、芳烃体系、卤代烃、有机混和物的反应及有机金属硼化合物的合成, 对金属蒸气合成法在金属有机合成中的应用进行了讨论。     

Total synthesis of apoptolidin: completion of the synthesis and analogue synthesis and evaluation

The total synthesis of apoptolidin (1) is reported together with the design, synthesis, and biological evaluation of a number of analogues. The assembly of key fragments 6 and 7 to vinyl iodide 3 via dithiane coupling technology was supplemented by a second generation route to this advanced intermediate involving a Horner-Wadsworth-Emmons coupling of fragments 22 and 25. The final stages of the synthesis featured a Stille coupling between vinyl iodide 3 and vinylstannane 2, a Yamaguchi lactonization, a number of glycosidations, and final deprotection. The developed synthetic technology was applied to the construction of several analogues including 74, 75, and 77 which exhibit significant bioactivity against tumor cells.     

Formal synthesis of nitidine through palladium-catalyzed isocoumarin synthesis

The isoquinolone intermediate 9 for the synthesis of nitidine was synthesized through palladium-catalyzed formation of isocoumarin 7 from o-styrylbenzoic acid derivative 5, which was prepared from palladium-catalyzed coupling reactions of aryl iodide 1 and 2 with vinylsilane.     

Studies towards the total synthesis of Sch 56036; isoquinolinone synthesis and the synthesis of phenanthrenes

The isoquinolinone hemisphere of Sch 56036 has been prepared using a modified Pomeranz-Fritsch reaction and the synthesis of the phenanthrene core has been modelled via a Suzuki coupling and subsequent ring closing metathesis.     

Tellurium in organic synthesis: synthesis of bioactive butenolides

Reduction of (Z)-β-butyltelluro-enones gives the corresponding γ-hydroxy vinylic tellurides with retention of the double bond configuration. Reaction of γ-hydroxy vinylic tellurides with 2 equiv of n-butyllithium produces 1,4-C,O-dianions, which on reaction with carbon dioxide give the corresponding butenolides.     

Radical-mediated synthesis of 3,4-dihydroisocoumarins: total synthesis of hydrangenol

A radically promoted synthesis of 3,4-dihydroisocoumarins has been achieved in moderate to good yields using titanocene(III) chloride (Cp₂TiCl) as the radical initiator. The total synthesis of (±)-hydrangenol has been completed using this radical technology. Cp₂TiCl was prepared in situ from commercially available titanocene dichloride (Cp₂TiCl₂) and Zn-dust in THF under argon.     

Benzothiazines in synthesis. Toward the synthesis of pseudopteroxazole

[reaction: see text] The tricyclic benzothiazine 15 was prepared in a straightforward fashion via a completely stereoselective intramolecular Friedel-Crafts alkylation. This compound represents a potential precursor to the antitubercular agent, pseudopteroxazole. Its synthesis proceeded via a completely selective, intramolecular addition of a sulfoximine-stabilized carbanion to an alpha,beta-unsaturated ester, followed by functional group manipulations.     

Benzothiazines in synthesis. A total synthesis of pseudopteroxazole

An enantioselective total synthesis of the naturally occurring antitubercular agent pseudopteroxazole is described. The synthesis is organized around the use of a stereoselective, intramolecular addition of a sulfoximine carbanion to an alpha,beta-unsaturated ester to form an enantiomerically pure benzothiazine. Other important processes include a completely stereoselective intramolecular Friedel-Crafts alkylation and a stereoselective and regioselective hydrogenation. [structure: see text]     

Formal synthesis of dictyostatin and synthesis of two dictyostatin analogues

A formal convergent synthesis of dictyostatin from (R)-Roche ester is described. Synthetic highlights include a Ni-catalyzed Nozaki-Hiyama-Kishi coupling between an aldehyde and a Z vinyl iodide to assemble the two main fragments, a diastereoselective Myers alkylation, a stereoselective Evans aldolization, two asymmetric Duthaler crotyltitanations, and a stereoselective Pd-catalyzed Marshall allenylindium addition to install the stereogenic centers of dictyostatin. The synthesis of (9R)-epi-dictyostatin and a new ring-contracted dictyostatin isomer were also achieved.     

生物质合成气一步法合成LPG的实验研究

由生物质气化合成液体燃料(甲醇、二甲醇和低碳烃类),是理想的碳中性绿色燃料,将其用作城市交通和民用燃料,已经引起全世界的广泛关注.[1,2]     

Recent developments in oligosaccharide synthesis: tactics,solid-phase synthesis and library synthesis

Oligosaccharides, commonly found on the cell surfaces, are deeply involved in a variety of important biological functions, yet demanding difficulties synthesizing such structures limit the investigation of their functions. Technologies to chemically synthesize these oligosaccharides have dramatically advanced during the last two decades mainly due to the introduction of good anomeric leaving groups. In addition, tactical analyses have been addressed to enhance the overall efficiency of oligosaccharide synthesis. Based on the advancement of solution-phase chemistry, solid-phase technologies are being investigated in connection with the current trend of combinatorial chemistry and high throughput screening. This review summarizes the necessary solution-phase methodologies, the status of solid-phase synthesis of oligosaccharides, and combinatorial synthesis of oligosaccharide libraries.     

Carotenoid synthesis by way of sulfones: synthesis of beta-carotene]

Sulfones, prepared from conjugated arylsulfonyl ylids and allylic halides, eliminate corresponding aryl sulfinates with formation of conjugated polyenes. Using this method β-carotene ( 8 ) has been synthesized.     

Total synthesis of plakortide E and biomimetic synthesis of plakortone B

The total synthesis of plakortide E (1a) is reported. A novel palladium-catalyzed approach towards 1,2-dioxolanes as well as an alternative substrate-controlled route leading exclusively to cis-highly substituted 1,2-dioxolanes have been developed. A lipase-catalyzed kinetic resolution was employed to provide optically pure 1,2-dioxolane central cores. Coupling of the central cores and side chains was achieved by a modified Negishi reaction. All four isomeric structures of plakortide E methyl ester, namely, 26a-d were synthesized. One of the structures, 26d, was shown to be identical with the natural plakortide E methyl ester on the basis of (1)H, (13)C NMR spectra and specific rotation comparisons. With the plakortide E methyl ester (4S,6R,10R)-(-)-cis-26d and its other three isomers in hand, we successfully converted them into (3S,4S,6R,10R)-plakortone B (2a), and its isomers ent-2a, 2b and ent-2b via an intramolecular oxa-Michael addition/lactonization cascade reaction. Finally, saponification converted 1,2-dioxolane 26d into plakortide E (1a) whose absolute configuration (4S,6R,10R) was confirmed by comparison of spectral and physical data with those reported.     

Biology-oriented synthesis

Which compound classes are best suited as probes and tools for chemical biology research and as inspiration for medicinal chemistry programs? Chemical space is enormously large and cannot be exploited conclusively by means of synthesis efforts. Methods are required that allow one to identify and map the biologically relevant subspaces of vast chemical space, and serve as hypothesis‐generating tools for inspiring synthesis programs. Biology‐oriented synthesis builds on structural conservatism in the evolution of proteins and natural products. It employs a hierarchical classification of bioactive compounds according to structural relationships and type of bioactivity, and selects the scaffolds of bioactive molecule classes as starting points for the synthesis of compound collections with focused diversity. Navigation in chemical space is facilitated by Scaffold Hunter, an intuitively accessible and highly interactive software. Small molecules synthesized according to BIOS are enriched in bioactivity. They facilitate the analysis of complex biological phenomena by means of acute perturbation and may serve as novel starting points to inspire drug discovery programs.     

Toward the synthesis of thapsigargin: enantioselective synthesis of 7,11-dihydroxyguaianolides

[reaction: see text] The enantioselective synthesis of a 7,11-dihydroxyguaianolide bearing the stereochemistry present in thapsigargin, a potent and selective inhibitor of the Ca(2+) SERCA-ATPase pumps, is described. Starting from (+)-dihydrocarvone, the synthesis presents two key steps. The first one involves the photochemical rearrangement of a gamma,delta-unsaturated ketone eudesmane into the corresponding guaiane. The second step consists of the regioselective oxidation of an unprotected tetrahydroxylated ketone to provide a dihydroxylactone with the required stereochemistry.     

Stereocontrolled synthesis of functionalized 1-azaspirans : Efficient synthesis of perhydrohistrionicotoxin

A formal total synthesis of perhydrohistrionicotoxin (H₁₂-HTX) is described based on a stereocontrolled α-acyliminium ion-olefin cyclisation. In the key step of the synthesis three asymmetric C atoms (C₆ C₇ and C₈) are introduced in a single operation leading to the formation of the spiro formate ester 15. Compound 15 is converted to the spirothiolactam alcohol 17, a known precursor of H₁₂-HTX.The versatility of the synthetic approach is further demonstrated by the stereocontrolled syntheses of other functionalized 1-azaspirans, viz the 6-Endo-Trig products 20 and 24 and the 5-Exo-Trig products 26 and 28. The formation of the latter two compounds is remarkable with respect to the mechanism.¹³C NMR data of a series of 1-azaspirans are provided, which inter alia show the existence of a conformational equilibrium in 1-azaspiro alcohol 16,Mass spectral criteria are used for assignment 5-Exo-or 6-Endo-cyclisation products.     

Combining two-directional synthesis and tandem reactions: synthesis of trioxadispiroketals

A tandem bromonium ion-promoted cyclization of two pendant hydroxyl groups onto a central furan core provides a highly direct route to both the [5,5,5]- and the [6,5,6]-trioxadispiroketal ring systems.     

Anion-templated synthesis

In contrast to the well-studied templating properties of cationic and neutral species there are relatively few examples of anion-templated syntheses. This is attributed to some of the intrinsic properties of anions such as their diffuse nature, pH sensitivity, and their relative high solvation free energies. However, the increasing number of anion-templated assemblies reported over the past few years demonstrates that these limitations are not as critical as first thought. This review summarizes the most important results on the use of anions as directing agents for the syntheses of a wide range of inorganic and organic assemblies (such as macrocycles, cages, helicates, rotaxanes, and extended structures). It is hoped that this will stimulate a closer look into this emerging area of supramolecular chemistry.