Divinyl Selenide Research Articles

First Examples of Reactions of 3-Trimethylsilyl-2-Propynamides and Organic Diselenides: Synthesis of Novel Derivatives of Propynamides

First examples of the reactions of 3-trimethylsilyl-2-propynamides with organic diselenides yielding 3-alkylselanyl-2-propenamides and 3-organylselanyl-2-propynamides were realized. The latter compounds were obtained by the Cu-catalyzed reaction of organic diselenides with 4-propioloylmorpholine. The reaction of 3-trimethylsilyl-2-propynamides with dialkyl diselenides in the system NaBH4/H2O/K2CO3/THF proceeded in a regio- and stereoselective fashion, affording 3-alkylselanyl-2-propenamides in 90–94% yields. An unsymmetrical divinyl selenide with the cyclic amide groups and a product, containing two selanyl-2-propenamide moieties and three cyclic amide groups, were synthesized. The Cu-catalyzed allylation reaction of 3-trimethylsilyl-2-propynamides was accompanied with desilylation to yield 3-allyl-2-propynamides.

Efficient Regioselective Synthesis of Novel Water-Soluble 2H,3H-[1,4]thiazino[2,3,4-ij]quinolin-4-ium Derivatives by Annulation Reactions of 8-quinolinesulfenyl Halides.

Regioselective synthesis of novel 2H,3H-[1,4]thiazino[2,3,4-ij]quinolin-4-ium derivatives has been developed by annulation reactions of 8-quinolinesulfenyl halides with vinyl chalcogenides (vinyl ethers, divinyl sulfide, divinyl selenide and phenyl vinyl sulfide) and tetravinyl silane. The novel reagent 8-quinolinesulfenyl bromide was used in the annulation reactions. The influence of the substrate structure and the nature of heteroatoms on the direction of the reactions and on product yields has been studied. The opposite regiochemistry was observed in the reactions with vinyl chalcogenides and tetravinyl silane. The obtained condensed heterocycles are novel water-soluble functionalized compounds with promising biological activity.

(Z,Z)-Selanediylbis(2-propenamides): Novel Class of Organoselenium Compounds with High Glutathione Peroxidase-Like Activity. Regio- and Stereoselective Reaction of Sodium Selenide with 3-Trimethylsilyl-2-propynamides.

The efficient regio- and stereoselective synthesis of (Z,Z)-3,3′-selanediylbis(2-propenamides) in 76–93% yields was developed based on the reaction of sodium selenide with 3-trimethylsilyl-2-propynamides. (Z,Z)-3,3′-Selanediylbis(2-propenamides) are a novel class of organoselenium compounds. To date, not a single representative of 3,3′-selanediylbis(2-propenamides) has been described in the literature. Studying glutathione peroxidase-like properties by a model reaction showed that the activity of the obtained products significantly varies depending on the organic moieties in the amide group. Divinyl selenide, which contains two lipophilic cyclohexyl substituents in the amide group, exhibits very high glutathione peroxidase-like activity and this compound is considerably superior to other products in this respect.

Catalyst-free selenylation of acylacetylenes with secondary phosphine selenides and water: A short-cut to bis(2-acylvinyl) selenides

Secondary phosphine selenides react with acylacetylenes in water to form bis(2-acylvinyl) selenides. The reaction proceeds without catalyst and organic solvent under mild conditions (70–72 °C, 3 h), the corresponding divinyl selenides being isolated as a mixture of (Z,Z)- and (E,Z)-isomers in a yield of up to 78%.

Green Hydroselenation of Aryl Alkynes: Divinyl Selenides as a Precursor of Resveratrol.

A simple and efficient protocol to prepare divinyl selenides has been developed by the regio- and stereoselective addition of sodium selenide species to aryl alkynes. The nucleophilic species was generates in situ, from the reaction of elemental selenium with NaBH4, utilizing PEG-400 as the solvent. Several divinyl selenides were obtained in moderate to excellent yields with selectivity for the (Z,Z)-isomer by a one-step procedure that was carried out at 60 °C in short reaction times. The methodology was extended to tellurium, giving the desired divinyl tellurides in good yields. Furthermore, the Fe-catalyzed cross-coupling reaction of bis(3,5-dimethoxystyryl) selenide 3f with (4-methoxyphenyl)magnesium bromide 5 afforded resveratrol trimethyl ether 6 in 57% yield.

Oxidation and halogenation of divinyl selenide. first synthesis of divinyl selenoxide

Efficient procedure was developed for the preparation of divinyl selenoxide in 92% yield by oxidation of divinyl selenide with sodium periodate. At the action of S-nucleophiles on the divinyl selenoxide it is reduced to divinyl selenide. The reaction of divinyl selenide with an equimolar amount of sulfuryl chloride or bromine led to halogenation products at the selenium atom: divinylselenium dichloride and divinylselenium dibromide. A rearrangement was discovered of divinylselenium dibromide into vinyl(1,2-dibromoethyl)-selenide. The hydrolysis of divinylselenium dichloride results in divinyl selenide.

ChemInform Abstract: Reaction of 2‐Pyridylselenenyl Bromide with Divinyl Selenide.

AbstractFirst time, in situ generated pyridylselenenyl bromide reacts with divinyl selenide to give vinylselanylselenazolopyridinium bromide (III) in a two‐step one‐pot procedure.

Reaction of 2-pyridylselenenyl bromide with divinyl selenide

Also published in Chemistry of Heterocyclic Compounds , 2012, 48 (7), pp 1129-1131 http://link.springer.com/article/10.1007/s10593-012-1115-y

One‐pot three‐component preparation of novel selenium‐containing spiroketals

The one‐pot three‐component preparation of novel selenium‐containing spiroketals with potential biological activity is described. When in situ prepared selenium dichloride is reacted with either propargyl or homopropargyl alcohols in the presence of acetone, two competitive reactions take place, namely 1,2‐addition to the triple bond with the formation of the corresponding functionalized divinyl selenides in a completely regio‐ and stereospecific manner and selenylation at the α‐position of the ketone, leading to the novel selenium‐containing spiroketals. An alternative approach to the synthesis of the selenium‐containing spiroketals with substantial increase of the chemical yield involves the reaction of alkynyl acetals with SeCl2. The structure of (4E,11E)‐4,11‐bis(chloromethylene)‐1,8‐dioxa‐5,12‐diselenaspiro[6.6]tridecane was unambiguously confirmed by X‐ray analysis. These novel selenium‐containing spiroketals were tested for regulation of glucose uptake in L6 myotubes. Copyright © 2012 John Wiley & Sons, Ltd.

ChemInform Abstract: Annulation of Phenyl Propargyl Ether with Selenium Dichloride.

AbstractThe selective preparation of the hitherto unknown dihydrobenzoxaselenine (II) is achieved.

Reaction of selenium dichloride with methacrylic acid

Selenium dichloride and dibromide in solution undergo disproportionation, so that they could not be isolated as individual substances [1]. Freshly prepared (in situ) selenium dichloride and dibromide are effective electrophilic reagents which are immediately involved in various transformations leading to organoselenium compounds [2–6]. We perform systematic studies on reactions of selenium dichloride and dibromide with compounds containing a double bond [3–5]. Reactions of selenium dihalides with divinyl sulfide [3] and divinyl selenide [4] give the corresponding Markovnikov addition products, 2,6-dihalo-1,4-thiaselenanes and -diselenanes, which undergo rearrangement into thermodynamically more stable 1,3-thiaselenolanes and -diselenolanes. Unlike vinyl sulfides and vinyl selenides, the double bond in vinyl sulfones is deactivated toward addition of electrophiles due to strong electron-withdrawing effect of the sulfonyl group. Selenium dihalides react with divinyl sulfone at a much lower rate as compared to divinyl sulfide, leading to fourand fivemembered heterocycles [6]. Methacrylic acid is a compound whose molecule contains a double bond and a strong electron-withdrawing group. Reactions of selenium halides with methacrylic acid were not studied. We examined the reaction of selenium dichloride with methacrylic acid at a molar ratio of 1 : 2 in acetonitrile at room temperature. Instead of expected 1 : 2 adduct we isolated in high yield (92%) a compound containing a diselenide moiety, previously unknown 2,2′-diselanediylbis(3-chloro-2-methylpropanoic acid) (I), whereas no analogous monoselenide was detected. Diselenide I was also obtained when Se2Cl2 was used instead of SeCl2; in this case, the reaction was accompanied by liberation of an equimolar amount of elemental selenium. The structure of diselenide I was confirmed by the H, C, and Se NMR and mass spectra and elemental analysis. It was isolated as two diastereoisomers at a ratio of 8 : 1. The observed coupling constant between the selenium atom and quaternary carbon atom (JSeC = 77 Hz for the major diastereoisomer) corresponds to direct coupling (JCSe) [7]. Thus the reaction of selenium dichloride with methacrylic acid is chemo-, regio-, and stereoselective, and it leads to the formation of diselenide I. Probable mechanism of this transformation is now under study. 2,2′-Diselanediylbis(3-chloro-2-methylpropanoic acid) (I). White powder, mp 121–122°C. H NMR spectrum, δ, ppm: major diastereoisomer: 1.52 s (6H, CH3), 3.85 d and 4.14 d (2H each, CH2Cl, J = 10.6 Hz); minor diastereoisomer: 1.53 s (6H, CH3), 3.81 d and 4.11 d (2H each, CH2Cl, J = 10.6 Hz). C NMR spectrum, δC, ppm: major diastereoisomer: 20.74 (CH3, JSeC = 16.2 Hz), 49.11 (CCH3, JCSe = 77 Hz), 51.29 (CH2Cl, JSeC = 15.1 Hz), 172.21 (C=O); minor diastereoisomer: 20.65 (CH3), 49.21 (CCH3), 51.29 (CH2Cl), 172.05 (C=O). Se NMR spectrum: major diastereoisomer: δSe 545 ppm; minor diastereoisomer: δSe 544 ppm. Mass spectrum (electron impact, 70 eV), m/z (Irel, %): 402 (4) [M] , 236 (10), 200 (7), ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 12, pp. 1889–1890. © Pleiades Publishing, Ltd., 2011. Original Russian Text © V.A. Potapov, S.V. Amosova, A.G. Khabibulina, L.I. Larina, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 12, pp. 1853–1854.

Annulation of phenyl propargyl ether with selenium dichloride

We are performing systematic studies aimed at the ap plication of novel reagents, such as selenium dichloride and dibromide, in the chemistry of organoselenium com pounds.1—6 Although these reagents cannot be isolated in pure state and undergo disproportionation in solutions7, it has been shown1 that freshly prepared selenium dichloride and dibromide can be used as selective electrophilic re agents in the synthesis of organoselenium compounds. The reactions of selenium dichloride and dibromide with acet ylene,2 diphenylacetylene,3 divinyl sulfide,4 divinyl sul fone,5 divinyl selenide,6 propargyl alcohols,8 2,3 di methoxybuta 1,3 diene9 have been studied. In contrast to selenium tetrahalides, whose reactions with organic sub stances often afford mixtures of products10, the reactions of selenium dihalides proceed selectively to afford the tar get compounds in high yields.1—6,8,9 The use of selenium dihalides for annulation of phenyl ethers containing unsaturated groups by combination of the addition to the unsaturated bond and electrophilic sub stitution in the ortho position of the benzene ring is of the utmost interest. There are no data on annulation of phenyl propargyl ether with selenium halides. We studied the reaction of selenium dichloride with phenyl propargyl ether and found the conditions that al low selective preparation of previously unknown E 3 chloromethylidene 2,3 dihydro 1,4 benzoxaselenine (1). The highest yield of product 1 (80%) was obtained upon mixing reagents at low temperature (–60 °C) in chloro form followed by heating the reaction mixture to the boil ing temperature of the solvent. One can assume that the addition of selenium dichlo ride to the propargyl group occurs at low temperature and the second step, viz., electrophilic aromatic substitution, requires heating of the reaction mixture. The structure of product 1 was established by 1H, 13C (including JMOD), and 77Se NMR spectroscopy and con firmed by the data from mass spectrometry and elemental analysis. The value of spin spin coupling constant (100 Hz) between the selenium atom and the double bond carbon atom having no protons corresponds to the C—Se direct constant (JC—Se), which is evidence of the addition of the selenium atom to the central carbon atom of the propargyl group. The E configuration of product 1 was established using the NOESY spectra. The regio and stereospecificity of the process can be explained by the fact that the reaction proceeds via the intermediate selenirenium ion А, which is attacked by the chloride ion at the sterically unshielded terminal car bon atom. Thus, we showed for the first time the possibility of annulation of the selenium containing heterocycles to the benzene ring based on the reaction of selenium dichloride with unsaturated organyl phenyl ethers, where the addi tion of selenium halides to the unsaturated bond of orga nyl phenyl ethers and electrophilic aromatic substitution is combined.

Reaction of selenium and tellurium halides with propargyl alcohols. The regio‐ and stereoselectivity of addition to the triple bond

AbstractA convenient method to incorporate selenium into an organic molecule is reported. Various aspects of the reaction of SeCl2 with propargyl alcohols, i.e., identity of reacting functionality, regiospecificity, and stereospecificity, differ from expectations based on known reactions of these alcohols with SCl2. Selenium dihalides undergo smooth 1,2‐addition to the triple bond of various propargylic alcohols resulting in the formation of the corresponding functionalized divinyl selenides in high yields and with complete regio‐ and stereospecificity. Of special mechanistic interest is the syn‐addition and anti‐Markovnikov orientation observed in all cases. Copyright © 2010 John Wiley & Sons, Ltd.

Reactions of selenium dichloride and dibromide with divinyl selenide: synthesis of novel selenium heterocycles and rearrangement of 2,6-dihalo-1,4-diselenanes

The synthesis of novel selenium heterocycles, 2,6-dihalo-1,4-diselenanes, 4-halo-2-halomethyl-1,3-diselenolanes and 2-halomethyl-1,3-diselenoles, based on the reactions of selenium dichloride and dibromide with divinyl selenide is described. The spontaneous rearrangement of 2,6-dihalo-1,4-diselenanes to 4-halo-2-halomethyl-1,3-diselenolanes is observed. Distillation of 4-chloro-2-chloromethyl-1,3-diselenolane leads to regioselective dehydrochlorination and the formation of 2-chloromethyl-1,3-diselenole.

Unexpected reaction of 4-bromo-2-bromomethyl-1,3-diselenolane with formation of divinyl selenide

Unexpected reaction of 4-bromo-2-bromomethyl-1,3-diselenolane with formation of divinyl selenide

Reactions of sodium selenide with ethynyl and bromoethynyl ketones: Stereo- and regioselective synthesis of functionalized divinyl selenides and 1,3-diselenetanes

A method for the preparation of 2,4-dimethylene-1,3-diselenetanes based on the novel reaction of sodium selenide with bromoethynyl ketones has been developed. New functionalized divinyl selenides have been obtained by regio- and stereoselective addition of sodium selenide to ethynyl ketones.

Theoretical conformational analysis of divinyl selenide

Theoretical conformational analysis of divinyl selenide was performed in terms of the Moller-Plesset second-order perturbation theory (MP2/6-311G**). Angular distribution of the probability density of populations of its rotational conformers was determined by analysis of the rotational potential energy surface. Divinyl sulfide was found to exist as an equilibrium mixture of three conformers having essentially nonplanar structure; the major conformer is syn-s-cis-s-trans, and the two others are syn- and anti-s-trans-s-trans with higher energy.

Divinyl selenide: conformational study and stereochemical behavior of its 77Se1H spin–spin coupling constants

Theoretical energy-based conformational analysis of divinyl selenide performed at the MP2/6-311G** level is substantiated by the second-order polarization propagator approach (SOPPA) calculations and experimental measurements of its (77)Se-(1)H spin-spin coupling constants, demonstrating marked stereochemical behavior in respect of the internal rotation of both vinyl groups around the Se-C bonds. Based on these data, divinyl selenide is shown to exist in an equilibrium mixture of three nonplanar conformers: one the preferred syn-s-cis-s-trans and two minor anti-s-trans-s-trans and syn-s-trans-s-trans forms.

Reaction of divinyl selenide with selenourea

Reaction of divinyl sulfide with thiourea proceeds in the presence of hydrochloric acid (EtOH/H2O/HCl) and leads to the formation of a cyclization product, 2H,6H-2,6-dimethyl-4-amino-1,3,5-dithiazinium hydrochloride [1, 2]. No data on the reaction of divinyl selenide with selenourea was published before, but it was presumable that under the same conditions it would be analogous to the above-mentioned process. Formation of the corresponding cyclic compound, diselenoazinium hydrochloride, could be expected. We have found that contrary to this suggestion the reaction of divinyl selenide with selenourea (EtOH/ H2O/HCl, 50–56oC) resulted in the formation of a previously unknown bis[1-carbamimidoylselanyl) ethyl] selenide dihydrochloride I, the product of selenourea addition to the double bonds of divinylselenide. At the double molar excess of selenourea in respect to the divinyl selenide the yield of compound I was quantitative.

Reaction of divinyl selenide with thiourea

Reaction of divinyl selenide with thiourea