Synthesis of (Z)-tetradec-11-en-1-ol and (Z)-hexadec-11-en-1-ol from dodecane-1,12-diol

A method has been developed for obtaining (Z)tetradec-11-en-1-ol and (Z)-hexadec-11-en-1-ol via dodec-11-yn-1-ol.     

Gas-phase reactions of NO3 and N2O5 with (Z)-hex-4-en-1-ol, (Z)-hex-3-en-1-ol ('leaf alcohol'), (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and (E)-hex-2-en-1-ol

The night-time atmospheric chemistry of the biogenic volatile organic compounds (Z)-hex-4-en-1-ol, (Z)-hex-3-en-1-ol ('leaf alcohol'), (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and (E)-hex-2-en-1-ol, has been studied at room temperature. Rate coefficients for reactions of the nitrate radical (NO(3)) with these stress-induced plant emissions were measured using the discharge-flow technique. We employed off-axis continuous-wave cavity-enhanced absorption spectroscopy (CEAS) for the detection of NO(3), which enabled us to work in excess of the hexenol compounds over NO(3). The rate coefficients determined were (2.93 +/- 0.58) x 10(-13) cm(3) molecule(-1) s(-1), (2.67 +/- 0.42) x 10(-13) cm(3) molecule(-1) s(-1), (4.43 +/- 0.91) x 10(-13) cm(3) molecule(-1) s(-1), (1.56 +/- 0.24) x 10(-13) cm(3) molecule(-1) s(-1), and (1.30 +/- 0.24) x 10(-13) cm(3) molecule(-1) s(-1) for (Z)-hex-4-en-1-ol, (Z)-hex-3-en-1-ol, (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and (E)-hex-2-en-1-ol. The rate coefficient for the reaction of NO(3) with (Z)-hex-3-en-1-ol agrees with the single published determination of the rate coefficient using a relative method. The other rate coefficients have not been measured before and are compared to estimated values. Relative-rate studies were also performed, but required modification of the standard technique because N(2)O(5) (used as the source of NO(3)) itself reacts with the hexenols. We used varying excesses of NO(2) to determine simultaneously rate coefficients for reactions of NO(3) and N(2)O(5) with (E)-hex-3-en-1-ol of (5.2 +/- 1.8) x 10(-13) cm(3) molecule(-1) s(-1) and (3.1 +/- 2.3) x 10(-18) cm(3) molecule(-1) s(-1). Our new determinations suggest atmospheric lifetimes with respect to NO(3)-initiated oxidation of roughly 1-4 h for the hexenols, comparable with lifetimes estimated for the atmospheric degradation by OH and shorter lifetimes than for attack by O(3). Recent measurements of [N(2)O(5)] suggest that the gas-phase reactions of N(2)O(5) with unsaturated alcohols will not be of importance under usual atmospheric conditions, but they certainly can be in laboratory systems when determining rate coefficients.     

Synthesis of Drim-9(11)-en-8α- and -8β-ols from Drimenol

Drim-9(11)-en-8α-ol and drim-9(11)-en-8β-ol were synthesized in six steps from drimenol. Drimenol was oxidized by P₂O₅ and DMSO to drimenal, which isomerized with p-TsOH into isodrimenal. Isodrimenal was reduced by NaBH₄ into isodrimenol, epoxidation of which by m-CPBA gave a mixture (3.4:1) of α- and β-epoxyisodrimenols. These reacted with tosyl chloride in Py to give a mixture of α- and β-epoxyisodrimenol tosylates. Treatment of the tosylate mixture with KI and then Ph₃P produced a mixture of drim-9(11)-en-8α- and -8β-ols that was separated chromatographically. The overall yield was ∼26%.__________Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 152–155, March–April, 2005.     

Stereocontrolled synthesis of 6-s-cis- and 6-s-trans-locked 9Z-retinoids by hydroxyl-accelerated Stille coupling of (Z)-tri-n-butylstannylbut-2-en-1-ol and bicyclic dienyl triflates

Analogues of 9-cis-retinoic acid with locked 6-s-cis and 6-s-trans conformations have been stereoselectively synthesized using a Stille coupling reaction between bicyclic dienyl triflates (5and 6, respectively) and (Z)-tributylstannylbut-2-en-1-ol (7) to stablish the Z geometry of the polyenic side chain. The mild conditions (25 degrees C, 30 min) of this coupling stand in contrast to the reluctance of the isomeric (E)-tributylstannylbut-2-en-1-ol (18) to react with triflates 5/6. The significant rate differences experimentally observed in Stille reactions between isomeric (Z)- and (E)-tri-n-butylstannylalkenols in favor of the former isomer, even with highly hindered alkenyl triflates, is ascribed to internal coordination of palladium to the heteroatom in the presumably rate-limiting transmetalation step. Dienals and trienals with an E geometry, which are not efficiently available by direct coupling of the corresponding triflates and E-stannanes, can in turn be obtained by isomerization of their Z-isomers.     

Eudesm-5-en-11-ol from Helichrysum italicum essential oil

Eudesm-5-en-11-ol was isolated from the oil of Helichrysum italicum and its structure was elucidated by 1D and 2D NMR spectroscopy.     

Oxidation of hexadec-11Z-en-1-ol by Cr(VI) reagents on polymeric supports

A method is proposed for the oxidation of hexadec-11Z-en-1-ol to hexadec-11Z-enal by Cr(VI) reagents on polymeric supports.A. S. Sadykov Institute of Bioorganic Chemistry, Uzbek Academy of Sciences, Tashkent. V. I. Lenin Tashkent State University. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 252–255, March–April, 1990.     

Synthesis of (E)-8-aza-11-deoxy-15α- and 15β-hydroxyprost-13-en-1-ol

The synthesis of a prostaglandin E₁ analog, (E)-8-aza-11-deoxy-15α- and 15β-hydroxyprost-13-en-1-ol, is reported.     

KO(t)Bu-promoted three-component coupling of aldehydes and alkynes: highly efficient synthesis of 1-en-4-yn-3-ols and 2-en-4-yn-1-ols

A KO(t)Bu-promoted three-component coupling reaction of aldehydes and alkynes without a transition-metal catalyst was developed in which the sequential addition/isomerization/addition processes take place in one pot. This reaction could be developed into a straightforward and effective method for rapid access to stereodefined (E)-1-en-4-yn-3-ol and (Z)-2-en-4-yn-1-ol compounds.     

Enantioselective synthesis of (1S,4R)-N-(benzylcarbamoyl)-4-aminocyclopent-2-en-1-ol by Candida antarctica lipase B

An efficient biocatalytic process has been developed to obtain optically pure (1S,4R)-N-(benzylcarbamoyl)- 4-aminocyclopent-2-en-1-ol which can be used as the key intermediate of ticagrelor. In this research, several N-(benzylcarbamoyl)-4-aminocyclopent-2-en-1-ol derivatives have been investigated in which Candida antarctica lipase B (CALB) was used to catalyze the asymmetric hydrolysis reaction. As expected, some of these substrates successfully gave (1S,4R)-N-(benzylcarbamoyl)-4-aminocyclopent- 2-en-1-ol in >98% enantiomeric excess (ee) with conversion yields up to 45%.     

Three new flavonoid glycosides, byzantionoside B 6'-O-sulfate and xyloglucoside of (Z)-hex-3-en-1-ol from Ruellia patula

Three new flavonoid glycosides, demethoxycentaureidin 7-O-β-D-galacturonopyranoside, pectolinarigenin 7-O-α-L-rhamnopyranosyl-(1?→4″)-β-D-glucopyranoside and 7-O-α-L-rhamnopyranosyl-(1?→4″)-β-D-glucuronopyranoside, a new megastigmane glucoside, byzantionoside B 6'-O-sulfate, and a new (Z)-hex-3-en-1-ol O-β-D-xylopyranosyl-(1″→2')-β-D-glucopyranoside, were isolated from leaves of Ruellia patula JACQ., together with 12 known compounds, β-sitosterol glucoside, vanilloside, bioside (decaffeoyl verbascoside), acteoside (verbascoside), syringin, benzyl alcohol O-β-D-xylopyranosyl-(1″→2')-β-D-glucopyranoside, cistanoside E, roseoside, phenethyl alcohol O-β-D-xylopyranosyl-(1″→2')-β-D-glucopyranoside, (+)-lyoniresinol 3α-O-β-D-glucopyranoside, isoacteoside and 3,4,5-trimethoxyphenol O-α-L-rhamnopyranosyl-(1″→6')-β-D-glucopyranoside. Their structures were elucidated by means of spectroscopic analyses.     

Heck reactions of aryl bromides with alk-1-en-3-ol derivatives catalysed by a tetraphosphine/palladium complex

cis,cis,cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C₃H₅)]₂ efficiently catalyses the Heck reaction of alk-1-en-3-ol with a variety of aryl bromides. In the presence of hex-1-en-3-ol or oct-1-en-3-ol, the β-arylated carbonyl compounds were selectively obtained. Linalool and 2-methylbut-3-en-2-ol led to the corresponding 1-arylalk-1-en-3-ol derivatives. Turnover numbers up to 69,000 can be obtained for this reaction. A minor electronic effect of the substituents of the aryl bromide was observed. Similar reaction rates were observed in the presence of activated aryl bromides such as bromoacetophenone and deactivated aryl bromides such as bromoanisole.     

Synthetic investigations in the field of attractive substances (sex attractants) of insects XI. Convenient synthesis of nonadec-cis-7-en-11-one and eicos-cis-7-en-11-one — Components of the sex pheromone of Carposina niponensis

A simple synthesis of the nonadec-cis-7-en-11-one and eicos-cis-7-en-11-one, components of the sex pheromone of the peach moth, has been performed from homopropargyl alcohols.All-Union Scientific-Research Institute of Biological Methods of Plant Protection, Kishinev. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 123–126, January–February, 1988.     

Synthesis of (Z/E)-11-tetradecen-1-ol, a component of Ostrinia nubilalis sex pheromone

11-Tetradecen-1-ol acetate is a mixture of geometric isomers with the Z/E-conformations in a 94:6 ratio that is used as an attractant to trap corn pests. It has a powerful attractive action similar to that of an isomeric mixture of 11-tetradecenyl acetate with the Z/E-conformation in a 95:5 ratio that was extracted from the peritoneal cavity of male Ostrinia nubilalis Hubner in Xinjing (PRC). __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 177–178, March–April, 2008.     

松毛虫性信息素(5Z,7E)-十二碳二烯醇的立体选择性合成

从简单原料乙炔出发,通过炔对丙烯醛的加成反应得到7-溴代-(4Z,6E)-庚二烯醛,再经乙二醇保护、Pd催化偶联、水解、Wittig反应和还原等步骤,立体选择性地得到松毛虫性信息素(5Z,7E)-十二碳二烯醇,其结构通过IR,NMR和MS等技术得到确认.     

Insect pheromones and their analogs

(Z)-hexadec-11-enal and (Z)-hexadec-11-1-yl acetate — components of the sex pheromone of insects of the generaHeliothis andManestra, respectively — have been synthesized by the condensation of undec-10-enal with hex-1-yne, deoxygenation of the heptadec-1-en-12-yn-11-ol formed via the corresponding tosylate to heptadec-1-en-12-yne, and the selective oxonolysis of the latter.Institute of Chemistry, Bashkir Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 440–444, May–June, 1987.     

An Improved Phenylselenoetherification of Pent-4-en-1-ol

The procedure employs phenylselenyl chloride or bromide, pent-4-en-1-ol, and additives, like pyridine and silver(I) salts, to generate the cyclic ether of tetrahydrofuran type in high yields. A catalytic amount of additive leads to higher yields, but equimolar amounts achieved almost quantitative yields under extremely mild experimental conditions. The effect of the halide ion of the selenylating reagent is not significant.     

Reinvestigation of the Nazarov cyclization of 1-(3-hydroxypropynyl)cyclododecan-1-ol to bicyclo[10.3.0]pentadec-1(12)-en-13-one

Reinvestigation of the acid-catalyzed cyclization of 1-(3-hydroxypropynyl)cyclododecan-1-ol under the conditions of the Nazarov reaction demonstrated that this conversion yields two isomeric bicyclic ketones, namely, bicyclo[10.3.0]pentadec-1(12)-en-13-one and bicyclo[10.3.0]pentadec-1-en-3-one. The latter compound is thermodynamically less stable. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1325–1327, July, 1997.     

An Improved Phenylselenoetherification of Pent-4-en-1-ol

Summary. The procedure employs phenylselenyl chloride or bromide, pent-4-en-1-ol, and additives, like pyridine and silver(I) salts, to generate the cyclic ether of tetrahydrofuran type in high yields. A catalytic amount of additive leads to higher yields, but equimolar amounts achieved almost quantitative yields under extremely mild experimental conditions. The effect of the halide ion of the selenylating reagent is not significant.     

Synthesis of (+)-drim-8-en-11-oic acid

A four-stage synthesis of (+)-drim-8-en-11-oic acid (IX) from norambreinolide (II) has been developed. The latter was converted by boiling with ethanolic sulfuric acid into a mixture of the methyl esters of bicyclohomofarnes-7- and -8-enoic acids which, on reaction with methyllithium, gave a mixture of 12-methyl-14,15,16-trinorlabd-7-and -8-en-12-ols. The alcohol with the ⁸ double bond was dehydrated with p-toluenesulfonic acid to 11-methyl-14,15,16-trinorlabd-8,11-diene, the ozoization of which yielded (+)-drim-8-en-11-oic acid.Institute of Chemistry, Academy of Sciences of the Moldavian SSR, Kishinev. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 214–221, March–April, 1991.     

Estrogenic Activity of Mycoestrogen (3β,5α,22E)-Ergost-22-en-3-ol via Estrogen Receptor α-Dependent Signaling Pathways in MCF-7 Cells

Armillariella tabescens (Scop.) Sing., a mushroom of the family Tricholomataceae, has been used in traditional oriental medicine to treat cholecystitis, improve bile secretion, and regulate bile-duct pressure. The present study evaluated the estrogen-like effects of A. tabescens using a cell-proliferation assay in an estrogen-receptor-positive breast cancer cell line (MCF-7). We found that the methanol extract of A. tabescens fruiting bodies promoted cell proliferation in MCF-7 cells. Using bioassay-guided fractionation of the methanol extract and chemical investigation, we isolated and identified four steroids and four fatty acids from the active fraction. All eight compounds were evaluated by E-screen assay for their estrogen-like effects in MCF-7 cells. Among the tested isolates, only (3β,5α,22E)-ergost-22-en-3-ol promoted cell proliferation in MCF-7 cells; this effect was mitigated by the ER antagonist, ICI 182,780. The mechanism underlying the estrogen-like effect of (3β,5α,22E)-ergost-22-en-3-ol was evaluated using Western blot analysis to detect the expression of extracellular signal-regulated kinase (ERK), phosphatidylinositol 3-kinase (PI3K), Akt, and estrogen receptor α (ERα). We found that (3β,5α,22E)-ergost-22-en-3-ol induced an increase in phosphorylation of ERK, PI3K, Akt, and ERα. Together, these experimental results suggest that (3β,5α,22E)-ergost-22-en-3-ol is responsible for the estrogen-like effects of A. tabescens and may potentially aid control of estrogenic activity in menopause.