Untitled

Ishmuratov, G. Yu.; Yakovleva, M. P.; Botsman, L. P.; Ишмуратова, Н. М.; Муслухов, Р. Р.; Khambalova, G. V.; Толстиков, Г. А.

doi:10.1023/a:1024172327822

Cited by 13 publications

(17 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Yield 0.35 g (70%), R f 0.18 (silica gel, petroleum ether-Et 2 O, 7 : 3). The IR and 1 H NMR spectra were identical to those reported in [10]. 13 C NMR spectrum (CDCl 3 ), δ C , ppm: 23.25 t (C 5′ ), 23.51 t (C 5 ), 24.58 t (C 3 ), 25.62 t (C 3′ ), 28.33 t (C 2′ ), 28.47 t (C 4 ), 28.82 t (C 4′ ), 29.77 q (C 8 , C 8′ ), 33.96 t (C 2 ), 43.30 t (C 6 .…”

Section: Methodssupporting

confidence: 67%

See 1 more Smart Citation

Synthesis of macrolides containing an azine or hydrazide fragment via successive tishchenko disproportionation and [1 + 1]-condensation

et al. 2011

Self Cite

View full text Add to dashboard Cite

Eight potentially useful 15-, 17-, 20-, and 22-25-membered macrolides having an azine or hydrazide fragment were synthesized starting from L-menthol, tetrahydropyran, and 4-methyltetrahydropyran via [1 + 1]-condensation of hydrazine hydrate and some dicarboxylic dihydrazides with 7-oxooctyl 7-oxooctanoate, 3-methyl-7-oxooctyl 3-methyl-7-oxooctanoate, and (3R)-3,7-dimethyl-6-oxooctyl (3R)-3,7-dimethyl-6-oxooctanoate obtained by the Tishchenko reaction from 7-oxo-, 3-methyl-7-oxo, and (3R)-3,7-dimethyl-6-oxooctanals, respectively. * For preliminary communications, see [1,2].It is known [3-6] that functionalized macrocyclic compounds are widely used in organic and petrochemical synthesis, detection and separation of metals by extraction, sorption and chromatographic analytical methods, ionometry, design of cardio-and psychotropic agents and studies on mechanisms of their action, development of antimicrobial, antiparasitic, and antitumor drugs, etc.In the present article we describe efficient ways of synthesis of 15-, 17-, 20-, and 22-25-membered macrolides having an azine or hydrazide fragment starting from accessible synthetic [tetrahydropyran (I) and 4-methyltetrahydropyran (II)] and natural [L-menthol (III)] compounds. The proposed approach is based on initial transformation of cyclic substrate into the corresponding oxo aldehydes, 7-oxo-, 3-methyl-7-oxo-, and (3R)-3,7-dimethyl-6-oxooctanals IV-VI, according to the procedure reported in [1,2], and their subsequent Tishchenko disproportionation to give dioxo esters VII-IX.[1+1]-Condensation of the latter with hydrazine hydrate or malonic, succinic, glutaric, and adipic acid dihydrazides in strongly dilute dioxane solution at room temperature, followed by treatment of the reaction mixture with methylene chloride-hexane (1 : 10), afforded 40-54% of macrolides having a ketone azine (X, XI) or bis-hydrazide fragment (XII-XVII), respectively (Schemes 1, 2).The structure of macrocyclic compounds X-XVII was determined by IR spectroscopy and 1 H and 13 C NMR; according to the HPLC data, their purity was ~95%. The NMR spectra of X-XVII were analyzed by comparing with the spectra of initial compounds, dioxo esters VII-IX and dicarboxylic acid dihydrazides. The 13 C NMR spectra of compounds XI and XVII lacked signals of carbonyl carbon atoms (δ C 214.13 and 214.42 ppm) and methylene and methine groups in the α-position to the carbonyl group (δ C 35.08, 37.53 ppm), which were typical of initial dioxo ester IX. In addition, no hydrazide NH 2 signal was observed in the 1 H NMR spectrum of macrocycle XVII (δ 4.75 ppm in the spectrum of the initial hydrazide). These findings indicate that the products have cyclic structure rather than the structure of acyclic substitution products. The 13 C NMR spectrum of XI, apart from the singlet at δ C 170.64 ppm (ester carbonyl carbon atom), contained a singlet at δ C 169.24 ppm due to C=N carbon atoms, which is consistent with the formation of macrocycle possessing an azine fragment.Compound XVII displayed in the 13 C NMR spectrum a signal ...

show abstract

Section: Methodssupporting

confidence: 67%

“…13 C NMR spectrum (CDCl 3 ), δ C , ppm: 23.25 t (C 5′ ), 23.51 t (C 5 ), 24.58 t (C 3 ), 25.62 t (C 3′ ), 28.33 t (C 2′ ), 28.47 t (C 4 ), 28.82 t (C 4′ ), 29.77 q (C 8 , C 8′ ), 33.96 t (C 2 ), 43.30 t (C 6 . The IR and 1 H NMR spectra were identical to those reported in [11].…”

Section: Methodssupporting

confidence: 67%

Synthesis of macrolides containing an azine or hydrazide fragment via successive tishchenko disproportionation and [1 + 1]-condensation

et al. 2011

Self Cite

View full text Add to dashboard Cite

show abstract

“…and also the application of key α,ω-diketones (3, 4) in the directed synthesis of a large variety of macroheterocycles with ester, azine and hydrazide functions, one of which [15,25-dimethyl-1,8-dioxo-16,17,23,24-tetraazacyclohentriaconta-15,24-dien-2,7,18,22-tetraone (10)] exhibited great antibacterial in vitro and in vivo activity [Butlerov Communications 2009, 16(4), 21-25 (in Russ.) [16,26-dimethyl-1,4,7-trioxa-17,18,24,25-tetraazacyclotetratriaconta-9,16,25,32-tetraen-8,19,23,34-tetraone (6), 8,22-dimethyl-1-oxa-9,10,20,21-tetraaza-8,21-cyclooctacosadien-2,11,19-trione (8), 8,23-dimethyl-1-oxa-9,10,20,22-teraaza-8,22-cyclononakosadien-2,11,20-trione (9), 4,25-dimethyl-28a,29,32,32a-tetrahydro-29,32-epoxy-11,18,2,3,26,27-benzadioxatetraazacyclotriaconta-3,25-dien-1,12,17,28- in its turn,3,4a,5,8, and separated from the reaction mixture. In our opinion, the introduction of pharmacophoric 7-oxabicyclo[2.2.1]heptane fragment [J. Med.…”

Section: An Area Of Application Of Tetrahydropyran Has Been Expanded mentioning

confidence: 99%

“…В углеродном спектре макроцикла 11, записан-ном в CDCl 3 при масс-спектрометрировании глубокого вакуума, то первоначально были получены спектры химической ионизации при атмосферном давлении (ХИАД, APCI, 20 эВ) с регистрацией положительных и отрицательных ионов на приборе LC MS 2010 фирмы «Shimadzu», содержащем соединение жидкостного хроматографа (жидкая подвижная фаза -вода, ацетонитрил) с масс-спектрометрическим детектором. При этом были зареги-стрированы весьма интенсивные пики протонированных MH + и депротонированных (M-H) -ионов, а также их ионные ассоциаты с 1÷3 молекулами воды.…”

Section: -16)unclassified

“…Ранее нами сообщалось о синтезе из тетрагидро-пирана (1) многофункционального феромона (2) [1] матки медоносной пчелы Apis melliphera L., дикетоэфира (3) [2] и дикетодиэфира (4) [4] и использовании ключевых α,ω-дикетонов (3, 4) в направленном синтезе целого ряда ма-крогетероциклов со сложноэфирными, азинной и гидра-зидными функциями, один из которых, 15,25-диметил-1,8-диоксо-16,17,23,24-тетраазациклогентриаконта-15,24-диен-2,7,18,22-тетраон, проявил значительную антибактериальную in vitro и in vivo активность. [4] В данном сообщении нами предложены эффектив-ные пути превращения доступного нефтехимического продукта -тетрагидропирана (1) -через промежуточные α,ω-дикетоны (3-5) в потенциально биологически и фар-макологически активные макрогетероциклы (6, 8, 9, 11) с эфирными и гидразидными функциями, в том числе и олефиновые.…”

Section: Introductionunclassified

See 1 more Smart Citation

Synthesis of Macroheterocycles with Ester and Hydrazide Fragments on the Basis of Tetrahydropyran

Ishmuratov¹,

Yakovleva²,

Mingaleeva³

et al. 2011

MHC

View full text Add to dashboard Cite

An area of application of tetrahydropyran has been expanded in the directed synthesis of macroheterocycles with ester and hydrazide fragments. The structures of the obtained macrocycles were proved by IR and NMR spectroscopy as well as mass spectrometry. We have already reported the synthesis of tetrahydropyran-based 9-oxo-2Е-decenoic acid(2) as the multifunctional pheromone [Chem. Nat. Compd. 2008, 44, 74-76] of queen honeybee Apis melliphera L., 7-oxooctyl-7-oxooctanoate (3) [Bashkir University Bulletin 2008, 3, 466-469 (in Russ.)] and bis (7-oxooctyl)adipate (4) [Butlerov Communications 2009, 17(5), 35-38 (in Russ.)] and also the application of key α,ω-diketones (3, 4) in the directed synthesis of a large variety of macroheterocycles with ester, azine and hydrazide functions, one of which [15,25-dimethyl-1,8-dioxo-16,17,23,24-tetraazacyclohentriaconta-15,24-dien-2,7,18,22-tetraone (10)] exhibited great antibacterial in vitro and in vivo activity [Butlerov Communications 2009, 16(4), 21-25 (in Russ.) [16,26-dimethyl-1,4,7-trioxa-17,18,24,25-tetraazacyclotetratriaconta-9,16,25,32-tetraen-8,19,23,34-tetraone (6), 8,22-dimethyl-1-oxa-9,10,20,21-tetraaza-8,21-cyclooctacosadien-2,11,19-trione (8), 8,23-dimethyl-1-oxa-9,10,20,22-teraaza-8,22-cyclononakosadien-2,11,20-trione (9), 4,25-dimethyl-28a,29,32,32a-tetrahydro-29,32-epoxy-11,18,2,3,26,27-benzadioxatetraazacyclotriaconta-3,25-dien-1,12,17,28- in its turn,3,4a,5,8, and separated from the reaction mixture. In our opinion, the introduction of pharmacophoric 7-oxabicyclo[2.2.1]heptane fragment [J. Med. Chem. 1985, 28, 1580-1590 Heterocycles 1978 Heterocycles , 9, 1749 Heterocycles -1757 ]. In this paper we put forward efficient methods to transform tetrahydropyran (1) as a disposable petrochemical product via intermediate α,ω-diketones [7-oxooctyl-7-oxooctanoate (3), bis(7-oxooctyl)adipate (4) and oxabis(ethan-1,2-diyl)(2'E,2'E)bis(9'-oxodec-2'-enoate) (5)] into potentially biologically and pharmacologically active macroheterocycles tetraone (11)] that contain the ester and hydrazide functions, including the olefin ones. The macrocycle (6) with conjugated ester groups was synthesized on the basis of unsaturated ketonic acid (2) by its transformation into the appropriate chloroanhydride, [2+1]-condensation with diethylene glycol and subsequent [1+1]-interaction between intermediate diketone diester (5) and glutaric dihydrazide. The synthesis of 28-(8) and 29-(9) member macrolides was performed by [1+1]-condensation of α,ω-dimethylketone (3) with azelaic and sebacic dihydrazides, respectively. The macrolide analog (10) exhibiting the antibacterial activity, i.e., macrocycle (11) with 7-oxabicyclo[2.2.1]heptane fragment in the form of a single di-exo-isomer, was obtained by [1+1]-condensation of the key precursor (4) with the linear dihydrazide of

show abstract

The Tishchenko Reaction

Koskinen

Kataja

2015

Organic Reactions

View full text Add to dashboard Cite

Aldehydes may be dimerized to symmetric esters via the Tishchenko reaction. This process is traditionally catalyzed by aluminum alkoxides, but a wide variety of different metal catalysts has been explored and implemented, ranging from simple alkali metal compounds to actinoid complexes. The mechanistic key step is a hydride transfer from a hemiacetal intermediate to an aldehyde, both participants being coordinated to the metal catalyst in the transition state. Recent research on the Tishchenko reaction has especially focused on the controlled synthesis of unsymmetrical esters. In the aldol‐Tishchenko variant, an aldol reaction takes place first between two aldehydes, or a ketone and an aldehyde. In the subsequent Tishchenko step, another aldehyde molecule coordinates to the aldol product, forming a hemiacetal intermediate. An intramolecular hydrogen transfer from the hemiacetal to the carbonyl group takes place, giving a 1,3‐diol monoester product. With ‐hydroxy ketone substrates, the reaction is highly diastereoselective towards 1,3‐ anti ‐diols due to a highly organized six‐membered transition state promoted by coordination of a metal catalyst to both the hemiacetal and carbonyl groups. Thus, recent research has strongly focused on the development of direct catalytic asymmetric aldol‐Tishchenko reactions. The Evans‐Tishchenko reaction is a further variant of the aldol‐Tishchenko reaction, being used to reduce preformed ‐hydroxy ketones to anti ‐1,3‐diols under relatively mild conditions. This method is applied to various total syntheses of natural products. Samarium iodide is commonly used as the catalyst, and nearly any aldehyde is suitable as the reducing agent. The reaction has also been exploited in a reverse fashion to oxidize complex aldehydes to carboxylic acids using a simple sacrificial ‐hydroxy ketone as the oxidant. This review covers the literature from the discovery of the Tishchenko reaction in 1887 up to early 2014. Different catalyst systems for both Tishchenko and aldol‐Tishchenko reactions are discussed and compared in the “Scope and Limitations” section, and the state of the art in substrate complexity for the reaction is presented in the “Tabular Survey”.

show abstract

Untitled

Cited by 13 publications

References 0 publications

Synthesis of macrolides containing an azine or hydrazide fragment via successive tishchenko disproportionation and [1 + 1]-condensation

Synthesis of macrolides containing an azine or hydrazide fragment via successive tishchenko disproportionation and [1 + 1]-condensation

Synthesis of Macroheterocycles with Ester and Hydrazide Fragments on the Basis of Tetrahydropyran

The Tishchenko Reaction

Contact Info

Product

Resources

About