Synthesis of new allenic prostanoids

New allenic prostanoids 5c, d, 7,9c, and 15b have been prepared by total synthesis. In each case a cuprate-propargylic acetate reaction was used as the key step.     

Synthesis of esters of allenic acids

Conclusions Starting with 1,1-dimethoxy-1-buten-3-yne, a method was proposed for the synthesis of the esters of -hydroxyallenic acids and of a 5-dialkylamino-2,3-pentadienoic acid.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2089–2090, September, 1971.     

Synthesis of functionalized chromans by PnBu3-catalyzed reactions of salicylaldimines and salicylaldehydes with allenic ester

P(n)Bu(3)-catalyzed cyclization reactions of salicylaldimines and salicylaldehydes with ethyl 2,3-butadienoate gave the corresponding functionalized chromans in moderate to good yields in THF under mild conditions. The new reaction provides a new method for the synthesis of biologically active chroman products.     

Allenes and acetylens—XXIII1: Synthesis of α-allenic amines via allenic imines obtained from organocopper reactions

N-2,3-alkadienyldiphenylmethanimines 5a-h are formed in moderate yields in 1,3-substitution reactions (S_N2′) of propargylic sulfonates with an organocopper reagent derived from metalated N-methyldiphenylmethanimine 1 and Me₂S·CuBr. The imines can be readily hydrolyzed to primary α-allenic amines. Alkylation of the imines with methyl fluorosulfonate followed by hydrolysis gives N-methyl-subsituted secondary α-allenic amines.     

联二烯丁基硫醚衍生物合成呋喃的反应

本文报道以联二烯丁基硫醚为起始物的呋喃衍生物的合成方法.实验结果表明,β-联二烯丁基硫醚醇在氢化钠的作用下以很高的收率环化生成一个苯硫基离去的呋喃产物,β-联二烯丁基硫醚醛与外加亲核试剂作用后能得到多一个取代的类似呋喃产物,而β-联二烯丁基硫醚酮在P2O5的促进下也能环化生成呋喃衍生物.     

Synthesis of furan from allenic sulfide derivatives

In this paper, we report the synthesis of furan derivatives from allenic sulfides. By the reaction with NaH, β-Hydroxyl allenic sulfides were found to generate furan products in excellent yields with the removal of phenylthio group. β-Aldehyde allenic sulfides were found to give similar furan products with one more substituent when treated with additional nucleophilic reagents. β-ketone allenic sulfides can also cyclize to give furan derivatives with the promotion of P₂O₅.     

Synthesis and properties of allenic natural products and pharmaceuticals

Nowadays, about 150 natural products comprising an allenic or cumulenic structure are known. The chemistry of these compounds has turned out to be a very attractive and prolific area of interest: advances in the isolation and characterization of new allenic natural products have led to the establishment of efficient synthetic procedures which in many cases also open up an access to enantiomerically pure target molecules. Inspired by the intriguing biological activities of many allenic natural products, allene moieties are now systematically introduced in pharmacologically active classes of compounds (steroids, prostaglandins, amino acids, nucleosides). The functionalized allenes thus obtained often exhibit impressive activities as mechanism-based enzyme inhibitors, cytotoxic, or antiviral agents. A prerequisite for further developments in this field is the efficient stereoselective synthesis of allene derivatives.     

Synthesis of functionalized 2H-1-benzopyrans by DBU-catalyzed reactions of salicylic aldehydes with allenic ketones and esters

[reaction: see text] DBU-catalyzed reactions of salicylic aldehydes with 3-methylpenta-3,4-dien-2-one, 3-benzylpenta-3,4-dien-2-one, or ethyl 2-methylbuta-2,3-dienoate gave the corresponding functionalized 2H-1-chromenes in good to excellent yields and good diastereoselectivities in some cases in DMSO, respectively.     

Synthesis of allenic thioethers of the pyridine series

-Picolyllithium and 2,6-lutidyllithium add to alkylthiovinylacetylenes to form adducts which, after demetallation with water, form allenic thioethers of the pyridine series.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3,pp. 354–355, March, 1971.     

Flash vacuum thermolysis of β-keto-trimethylsilyl-enol-ethers: Synthesis of allenic and furanic derivatives

Thermolysis at 800° of a series of β-keto-trimethylsilyl-enol-ethers allows the elimination of a trimethylsilanol molecule through a 1,5 rearrangement. The reaction products are furanic derivatives, which are obtained in often good yields through an allenic intermediate, which has been isolated.     

Synthesis of n-vinyloxyethylated amides and ureas

Conclusions N-Vinyloxyethylated amides were synthesized by reacting the vinyl ethers of amino and ketimino alcohols with the acid chlorides of the 2,4-dichlorophenoxyacetic, o-, and p- chlorobenzoic acids, while the previously unknown N-vinyloxyethylated derivatives of ureas were obtained from the vinyl ethers of amino alcohols and aryl isocyanates.Translated fron Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1893–1896, August, 1981.     

Synthesis and properties of phenylogous amides

Vinylogy is a widely accepted principle involving the transfer of electronic chemical character through a double bond, and many reactions have been developed by applying this concept. In contrast, phenylogy, which involves the connection of two substituents through a benzene ring, is rarely recognized as a related idea. In this article, we present synthesis and physical properties, including their structure and reactivity of phenylogous amides. This amide mimetic unit is relatively stable and easily prepared by the Hartwig–Buchwald amination reaction. The effect of the resonance was examined by means of crystallography, reactivity and UV–vis spectroscopy.     

Synthesis and biological evaluation of allenic quinazolines using palladium-catalyzed hydride-transfer reaction

Allenic quinazolines 13a-h were designed as mimics of Tarceva, which is an epidermal growth factor receptor (EGFR) tyrosine kinase inhibitor, and synthesized from the corresponding 4-(iodoanilino)quinazolines or 4-(iodophenoxy)quinazolines with N,N-dicyclohexylprop-2-ynylamine by the Sonogashira coupling followed by palladium-catalyzed hydride-transfer reaction. Cell growth inhibition of 13a-h toward A431, Kato III, SKBR3, and HepG2 was examined. Among the compounds synthesized, 13a showed a similar cell growth inhibition to Tarceva. Moreover, 13d and 13h exhibited a specific growth inhibition toward Kato III cells (IC₅₀ = 12 and 4.7 μM, respectively), although a significant inhibition toward other three cell lines was not observed at a 100 μM concentration of compounds.     

Synthesis of nitroxylcarbamidophosphoric acid amides

A method for obtaining new organophosphorus nitroxyls was developed based on Kirsanov's phosphazo reaction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1139–1141, May, 1990.     

Synthesis of α,β-unsaturated butenolides from allenic acids

The electrophile-initiated cyclisation of allenic acids and esters provides a general route for the synthesis of β-substituted α,β-unsaturated butenolides.     

Synthesis of thiophosphoric acid amides

Conclusions The cyclohexylamido- and piperididothiophosphoric acids were obtained for the first time, and also piperazido-N,N-bisthiophosphoric acid as the Na and NH₄ salts.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2402–2403, October, 1982.