Ammonium eneselenolates: stereochemistry and electronic properties.

Ammonium eneselenolates were generated with high efficiency by reacting selenothioic acid S-esters with a THF solution of TBAF. The methylation of ammonium eneselenolates gave ketene selenothioacetals as stereoisomeric mixtures. The ratio of the two stereoisomers depended on the duration of the reaction before the addition of MeI. Ammonium eneselenolates were characterized by examining their (1)H, (13)C, and (77)Se NMR spectra, which indicated that ammonium eneselenolates were present almost exclusively as Z-isomers. These results suggested that ammonium eneselenolates are kinetically generated as stereoisomeric mixtures, and isomerization of E-isomers to Z-isomers then takes place to result in the exclusive formation of Z-isomers. During the methylation of Z-isomers of ammonium eneselenolates, the isomerization of Z-isomers to E-isomers occurs to give stereoisomeric mixtures of ketene selenothioacetals. NMR spectra of ammonium eneselenolates implied that the electrons at the selenium atom are somewhat delocalized to the carbon-carbon double bond and the carbon-selenium bond shows partial double-bond character.     

Synthesis and E/Z configuration determination of novel derivatives of 3-aryl-2-(benzothiazol-2'-ylthio) acrylonitrile, 3-(benzothiazol-2'-ylthio)-4-(furan-2'-yl)-3-buten-2-one and 2-(1-(furan-2'-yl)-3'-oxobut-1'-en-2-ylthio)-3-phenylquinazolin-4(3H)-one

Knoevenagel condensation of 2-(benzothiazol-2-ylthio) acetonitrile (2) with either furan-2-carbaldehyde or thiophene-2-carbaldehydes leads to E-isomers 4a-b exclusively, while the condensation of the compound 2 with benzaldehyde or para-substituted benzaldehydes with an electron-donating group afforded E/Z mixtures 4c-e with preferentially formation of the E-isomer. Condensation of furan-2-carbaldehyde (3a) with either 1-(benzothiazol-2'-ylthio) propan-2-one (5) or 2-(2'-oxo propylthio)-3-phenyl-quinazolin-4(3H)-one (9) leads exclusively to the Z-isomers of 6 and 10, respectively. The structures of the newly synthesized compounds were elucidated by elemental analyses, 1H-NMR and 13C-NMR spectra, COSY, HSQC, HMBC, NOE, MS and X-ray crystallographic investigations.     

New practical synthesis of indazoles via condensation of o-fluorobenzaldehydes and their O-methyloximes with hydrazine

The reaction of o-fluorobenzaldehydes and their O-methyloximes with hydrazine has been developed as a new practical synthesis of indazoles. Utilization of the methyloxime derivatives of benzaldehydes (in the form of the major E-isomers) in this condensation effectively eliminated a competitive Wolf-Kishner reduction to fluorotoluenes, which was observed in the direct preparations of indazoles from aldehydes. Reaction of Z-isomers of methyloximes with hydrazine resulted in the formation of 3-aminoindazoles via a benzonitrile intermediate.     

Reversible photoswitching of the coordination numbers of silicon in organosilicon compounds bearing a 2-(phenylazo)phenyl group

Several organosilicon compounds bearing a 2-(phenylazo)phenyl group were synthesized from the corresponding chlorosilanes and 2-lithioazobenzene prepared by halogen-lithium transmetalation of 2-iodoazobenzene. Their structures were determined by (1)H, (13)C, (19)F, and (29)Si NMR spectra, UV-vis spectra, and X-ray crystallographic analyses. In the UV-vis spectra, silyl groups caused red shifts of both the n-pi and pi-pi transitions of the azo group compared with the transitions of the unsubstituted azobenzene. The E-isomers of the fluorosilanes showed an intramolecular interaction between a nitrogen atom of the azo group and the silicon atom, leading their intermediate structures between a distorted trigonal bipyramidal structure and a tetrahedral structure around the silicon atoms, which were revealed by the X-ray crystallographic analyses and the NMR spectra. On the other hand, silanes without fluorine atoms showed tetrahedral structures in the absence of such an interaction. The photoirradiation of the E-isomers of the fluorosilanes afforded reversibly the corresponding Z-isomers in good yields. The silicon atoms of the Z-isomers were found to be tetracoordinate in the absence of Si-N interactions by the (29)Si NMR spectra. The coordination numbers of the silicon atom of the fluorosilanes were reversibly switched between four and five by photoirradiation. These properties were compared to those of a tetrafluoro[2-(phenylazo)phenyl]silicate.     

In-solution and on-plate light-catalyzed E/Z isomerization of cyclic chalcone analogues. Lipophilicity of E- and Z-2-(X-benzylidene)-1-benzosuberones

Some cyclic chalcone analogues [E-2-(X-benzylidene)-1-indanones, -tetralones, and -benzosuberones], on-plate UV light-catalyzed formation of new chromatographic spots, can be observed during thin-layer chromatography (TLC). Gas chromatographic (GC) analysis of selected derivatives indicates the formation of one new substance in each case. GC coupled with mass spectrometry and 1H NMR analysis of the samples reveals that the compounds formed are the respective Z-2-(X-benzylidene)-1-indanones, -tetralones, and -benzosuberones. Two-dimensional TLC shows that the E/Z isomerization is a reversible process. By means of the RP-TLC, the logarithm of n-octanol-water partition coefficient (log P) values of E- and Z-isomeric pairs of selected 2-(X-benzylidene)-1-benzosuberones is determined. The Z-isomers are less lipophilic than the E-isomers.     

Rhodium-catalyzed stereoselective formation of Z-enamines from allylaziridines

Rhodium (I)-catalyzed isomerization of N-allylaziridines affords isolable Z-enamines in excellent yields and with high stereoselectivity. Cationic [Rh(BINAP)(COD)]OTf and RhH(CO)(PPh3)3 follow the same selectivity toward the Z-isomers. This selectivity is not observed with other N-allylamines which give the thermodynamically more stable E-isomers. These unexpected results suggest a possible deviation from the commonly accepted mechanism of isomerization. Preliminary results show that the Z-enamines undergo cycloaddition with DMAD to form highly strained N-cyclobutenyl aziridines.     

Synthesis and stereoisomerism of derivatives of <Emphasis Type="Italic">tert</Emphasis>-butyl 7-alkylideneceph-3-em-4-carboxylate

By condensation of tert-butyl 3-methyl-7-oxoceph-3-em-4-carboxylate and its 3-acetoxymethyl analog with acetylmethylenetriphenylphosphorane and 3-trimethylsilylpropyn-2-ylindenetriphenylphosphorane tert-butyl 7Z-acetylmethylene-3-methylceph-3-em-4-carboxylate and also 7Z-and 7E-isomers of tert-butyl 3-acetoxymethyl-7-(3-trimethylsilylpropyn-2-ylidene)ceph-3-em-4-carboxylates were synthesized. Oxidation of these compounds with 1 equivalent of meta-chloroperbenzoic acid gave their 1R-and 1S-sulfoxides, and oxidation with 2 equivalents gave the corresponding sulfones. According to data from ¹H NMR spectroscopy, the carbonyl of the β-lactam descreens proton H-9 of the alkylidene group in the 7Z-isomers more strongly than in the 7E-isomers, shifting their signals to weaker field. Analogous shifts of the H-6 signal to weaker field was observed in the 1R-sulfoxides in comparison with that for the 1S-sulfoxide. These results were confirmed by X-ray crystallography of tert-butyl 7Z-acetylmethylene-3-methyl-1S-oxoceph-3-em-4-carboxylate and tert-butyl 7Z-acetylmethylene-3-methyl-1,1-dioxoceph-3-em-4-carboxy-late. In memory of Professor A.A. Potekhin __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, 618–626, April, 2008.     

Structural requirements in chiral diphosphine-rhodium complexes. X asymmetric homogeneous hydrogenation of z-N-acetyldehydroamino acids and esters with (1R,2R)-trans-1,2-bis(diphenylphosphinomethyl)cyclobutane/rhodium(I) complexes.

Z--acetamidocinnamate esters were hydrogenated with neutral rhodium(I) complexes containing (1R,2R)-trans-1,2-bis(diphenylphosphinomethyl)cyclobutane. Increasing the steric bulk of the alcohol moiety in the unsaturated esters had little influence upon the optical purity of the N-acetylphanylalanine ester products. In the series Me, Et, i-Pr, and t-Bu the optical purity decreased from 44 % ee-(R) [Me] to 40 % ee-(R) [t-Bu]. The chiral cyclobutane diphosphine appears to be only slightly more effective than the heterocyclic DIOP when ring-substituted Z--acetamidocinnamic acids are hydrogenated with neutral rhodium(I) complexes without the addition of triethylamine. Addition of triethylamine to the solvent blend seems to be more beneficial to the cyclobutane analogue than to DIOP.     

Synthesis and Antifeeding Activity of Acetylene-Containing Tonghaosu Analogs

During our continuous efforts towards the search for environmental benign insect antifeedant, we established a concise method for the synthesis of Tonghaosu, a naturally occurring antifeedant.[1] Herein, we report the synthesis and antifeeding activity of 22 new tonghaosu analogs, which contain varied B ring as well as one or two acetylene functionalities. Preliminary bioassay indicates that two acetylene groups containing tonghaosu analogs have better antifeedant activity against large white butterfly (Pieris brassicae L.) than those with one acetylene group. More interestingly,Z-isomers are much more active than their corresponding E-isomers.     

Green Monomer of CO_2 and Alkyne-based Four-component Tandem Polymerization toward Regio-and Stereoregular Poly(aminoacrylate)s

Green monomers, such as carbon dioxide(CO_2), are closely related to our daily life and highly desirable to be transferred to functional polymers with diverse structures and versatile properties because they are abundant, cheap, nontoxic, renewable, and sustainable. However, the polymerizations based on these green monomers are to be further developed. In this work, a facile CO_2 and alkyne-based one-pot, two-step, fourcomponent tandem polymerization was successfully established. The polymerization of CO_2, diynes, alkyl dihalides, and primary/secondary amines can proceed under mild reaction conditions and regio-and stereoregular poly(aminoacrylate)s with good solubility and thermal stability were obtained in high yields(up to 95%). Notably, distinctly different stereoregularity of resultant poly(aminoacrylate)s was realized via using primary or secondary amines. Using the former would readily generate polymers with 100% Z-isomers, whereas the latter furnished products with over 95% E-isomers. Through different monomer combination, the polymers with tunable structures and properties were obtained.Moreover, the tetraphenylethene units containing poly(aminoacrylate)s, showing the unique aggregation-induced emission characteristics,could function as a fluorescent probe for sensitive explosive detection. Thus, this work not only develops a facile CO_2 and alkyne-based multicomponent tandem polymerization but also provides a valuable strategy to fine-tune the polymer structures and properties, which could be potentially applied in diverse areas.     

Stereochemistry of the Horner-Emmons reaction of 3-functionalized 2-methyl-2-propenylphosphonates with aliphatic aldehydes 5. Effects of base anion,temperature, solvent,and addition of a crown ether

Taking the reaction of diethyl 3-ethoxycarbonyl-2-methyl-2-propenylphosphonate with 3-methylbutanal as an example, it has been shown that the composition of the equilibrium mixture of the E- and Z-isomers of the starting phosphonate formed in the presence of bases is independent of the base anion (KOH or K₂CO₃) and the solvent (benzene or DMSO). In the mixture of 2E,4E- and 2Z,4E-isomers of ethyl 3, 7-dimethyl-2, 4-octadienoate formed in this reaction, the proportion of the 2E, 4E-ester falls as the temperature is reduced from +40 to –40C; the proportion of the 2E, 4E-ester in the heterophase system base/aprotic solvent increases with increasing polarity; and in the presence of 10 mole % of 18-crown-6 ether the proportion of the 2E, 4E-isomer is increased, being greater than 50% in all solvents. These findings indicate that the stereochemical outcome of the reaction depends on the balance between the phase systems and the chemical equilibria, including the formation, dissociation, and reactions of the intermediate products.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2544–2550, November, 1990.     

Camphor and nopinone derivatives as new photosensitive chiral dopants

E-Z photoisomerizable chiral dopants are a class of materials that can be used to prepare birefringent optical components with patterned optical properties. Two new photoisomerizable chiral dopants have been synthesized and analysed. The materials were derived from nopinone and camphor. The properties of these compounds were compared with the properties of the methone derivative described in earlier publications. The E-isomers of the nopinone and camphor derivatives had helical twisting powers of 2.7 and 1.7 μm^-1, respectively. This is a factor of about 10 lower than the value obtained for the menthone derivative (-19 μm^-1). Due to the high absorption of the Z-isomers relative to the E-isomers of the nopinone and camphor derivatives, isomerization during 365 nm UV exposure proceeded to a much lesser extent than the isomerization of the menthone derivative. At shorter wavelengths, the absorption of the Z-isomer is much lower than that of the E-isomer and much higher degrees of conversion could be achieved.     

Dialkoxyphosphinyl-substituted enols of carboxamides

Reactions of isocyanates XNCO (e.g., X = p-An, Ph, i-Pr) with (MeO)2P(=O)CH2CO2R [R = Me, CF3CH2, (CF3)2CH] gave 15 formal "amides" (MeO)2P(=O)CH(CO2R)CONHX (6/7), and with (CF3CH2O)2P(=O)CH2CO2R [R = Me, CF3CH2] they gave eight analogous amide/enols 17/18. X-ray crystallography of two 6/7, R = (CF3)2CH systems revealed Z-enols of amides structures (MeO)2P(=O)C(CO2CH(CF3)2)=C(OH)NHX 7 where the OH is cis and hydrogen bonded to the O=P(OMe)2 group. The solid phosphonates with R = Me, CF3CH2 have the amide 6 structure. The structures in solution were investigated by 1H, 13C, 19F, and 31P NMR spectra. They depend strongly on the substituent R and the solvent and slightly on the N-substituent X. All systems displayed signals for the amide and the E- and Z-isomers. The low-field two delta(OH) and two delta(NH) values served as a probe for the stereochemistry of the enols. The lower field delta(OH) is not always that for the more abundant enol. The % enol, presented as K(enol), was determined by 1H, 19F, and 31P NMR spectra, increases according to the order for R, Me < CF3CH2 < (CF3)2CH, and decreases according to the order of solvents, CCl4 > CDCl3 approximately THF-d8 > CD3CN >DMSO-d6. In DMSO-d6, the product is mostly only the amide, but a few enols with fluorinated ester groups were observed. The Z-isomers are more stable for all the enols 7 with E/Z ratios of 0.31-0.75, 0.15-0.33, and 0.047-0.16 when R = Me, CF3CH2, and (CF3)2CH, respectively, and for compounds 18, R = Me, whereas the E-isomers are more stable than the Z-isomers. Comparison with systems where the O=P(OMe)2 is replaced by a CO2R shows mostly higher K(enol) values for the O=P(OMe)2-substituted systems. A linear correlation exists between delta(OH)[Z-enols] activated by two ester groups and delta(OH)[E-enols] activated by phosphonate and ester groups. Compounds (MeO)2P(=O)CH(CN)CONHX show 相似文献   

Enols of amides activated by the 2,2,2-trichloroethoxycarbonyl group

Reaction of isocyanates XNCO (X = Ar, i-Pr, t-Bu) with CH(2)(Y)CO(2)CH(2)CCl(3) (Y = CO(2)Me, CO(2)CH(2)CCl(3), CN) gave 15 amides XNHCOCH(Y)CO(2)CH(2)CCl(3) (6) or enols of amides XNHC(OH)=C(Y)CO(2)CH(2)CCl(3) (5) systems. The amide/enol ratios in solution depend strongly on the substituent Y and the solvent and mildly on the substituent X. The percentage of enol for group Y increases according to Y = CN > CO(2)CH(2)CCl(3) > CO(2)Me and decreases with the solvent according to CCl(4) > C(6)D(6) > CDCl(3) > THF-d(8) > CD(3)CN > DMSO-d(6). With the most acidic systems (Y = CN) amide/enol exchange is observed in moderately polar solvents and ionization to the conjugate base is observed in DMSO-d(6). The solid-state structure of the compound with Y = CN, X = i-Pr was found to be that of the enol. The reasons for the stability of the enols were discussed in terms of polar and resonance effects. Intramolecular hydrogen bonds result in a very low delta(OH) and contribute to the stability of the enols and are responsible for the higher percentage of the E-isomers when Y = CO(2)Me and the Z-isomers when Y = CN. The differences in delta(OH), delta(NH), K(enol), and E/Z enol ratios from the analogues with CF(3) instead of CCl(3) are discussed.     

Substituent effects on the Z/E-selectivity in cross-metathesis of conjugated enynes

Cross-metathesis of a range of conjugated enynes with alkenes turns out to proceed with preferential formation of Z-isomers over E-isomers up to >25:1. Careful studies including substrate modification and control experiments revealed that the reaction proceeds under kinetic rather than thermodynamic control. Driving forces for this substrate-dependent Z-selectivity are attributed to the steric hindrance between substituents on the reacting enynes and NHC ligand of the ruthenium catalyst in the putative metallacyclobutane, as well as chelation effects of suitably positioned functional groups to Ru, which is strongly supported by ab initio calculations.     

Gas chromatographic enantiomer separation of chiral ketones — Order of elution and configurational stability of oxime derivatives

Summary Oximes of chiral ketones can be separated into enantiomers by capillary gas chromatography on the chiral polysiloxanes XE-60-L-valine-(S)- or (R)--phenylethylamide. Usually predominantly E-isomers are formed and are better separated than Z-isomers. From time-dependent gas chromatographic measurements it can be concluded that the oximes are configurationally stable and that racemization during oxime formation is negligible. The order of elution of enantiomers depends on the structure of the ketone and is different for aliphatic and alicyclic compounds.     

Synthesis of novel 1,3,5-tris(arylazo)benzenes via Pd-catalyzed couplings and Cu(I)-mediated direct oxidations

A series of novel 1,3,5-tris-azobenzenes were prepared from 1,3,5-trihalobenzene via Pd-catalyzed couplings of N-Boc aryl hydrazines and subsequent Cu(I)-mediated direct oxidations. The oxidation of tris-arylhydrazide provided the azobenzene as a mixture of all four of the possible E/Z-isomers; [E,E,E]-, [E,E,Z]-, [E,Z,Z]-, and [Z,Z,Z]-1,3,5-tris-azobenzenes. A slow removal of the solvent in the dark transformed the isomers into the all-trans, [E,E,E]-isomer.     

1—间甲氧苯基—2—二甲胺甲基环己醇的合成与结构研究

通过间溴苯甲醚与２－二甲胺甲基环己酮反应制得１－间甲氧苯基－２－二胺甲基环己醇，对其分离得到相应的顺反异构体，对反应的立体化学进行了分析，并对＾１３Ｃ ＮＭＲ谱确定了顺反异构体的构型。     

Stereoselective Synthesis of (Z)-1-Benzhydryl-4-cinnamylpiperazines via the Wittig Reaction

A synthetic method of producing (E)- and (Z)-isomers of 1-benzhydryl-4-cinnamylpiperazines in a specific ratio from corresponding benzhydrylpiperazine is described. Of the three compounds synthesized (5a–c), the ratio of E/Z-isomers remained around 15:85. The key intermediates, 1-benzhydryl-4-(2,2-dimethoxyethyl)piperazine derivatives (3a–c), were prepared by nucleophilic substitution reaction of benzhydrylpiperazines (2a–c) with chloroacetaldehyde dimethylacetal in good yield (up to 88%). Hydrolysis of 3a–c gave the corresponding aldehydes 4a–c, which when subjected to the Wittig reaction followed by column purification to afford 1a–c (E-isomers) and 6a–c (Z-isomers) in pure form. The isolated compounds were characterized by NMR and mass spectral analysis.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Synthesis of substituted thiophenes and thiazolidines from 1-amino-2-benzoyl-2-(1-pyridinio)ethylene-1-thiolates

It was found that alkylation of Z-isomers of 1-amino-2-benzoyl-2-(1-pyridinio)-ethylene-1-thiolate with phenacyl bromides proceeds regioselectively with formation of Z-isomers of bromides of 1-amino-2-benzoyl-2-(1-pyridinio)-1-phenacylthioethylenes, which are used in the synthesis of not easily accessible thiophenes and thiazolidines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1637–1642, July, 1991.