(1-Methoxyvinyl)boronic and (1-chlorovinyl)boronic esters

(s)-Pinanediol (1-methoxyvinyl)boronate ( 1 ) was prepared from (1-methoxyvinyl)-lithium and triisopropyl borate followed by (s)-pinanediol. Attempted reaction with (dichloromethyl)lithium failed, and reaction with butylmagnesium chloride followed by acetic acid yielded a mixture of diastereomers of (s)-pinanediol (1-methoxy-1-methyl-pentyl)boronate ( 2 ). (s)-Pinanediol (1-chlorovinyl)boronate ( 4 ) has been prepared by dehydrochlorination of (s)-pinanediol 1,1-dichloroethylboronate ( 3 ) with lithium chloride in dimethylformamide. Reaction of 4 with (dichloromethyl)lithium yielded (s)-pinanediol (1S)-(1,2-dichloroallyl)boronate ( 5 ) in 92% diastereomeric excess. Reaction of 5 with RMgX resulted in a 3 : 1 ratio of displacement of the 1-Cl from carbon by R to displacement of the entire 1,2-dichloroallyl group from boron by R. With lithium benzyl oxide, displacement of the 1-Cl from 5 failed entirely. Reaction of 4 with (dibromomethyl)lithium was inefficient and yielded a gross mixture of diastereomers.     

The 1 (2)A(1), 1 (2)B(2), and 1 (2)A(2) states of the SO(2) (+) ion studied using multiconfiguration second-order perturbation theory

The 1 (2)A(1), 1 (2)B(2), and 1 (2)A(2) electronic states of the SO(2) (+) ion have been studied using multiconfiguration second-order perturbation theory (CASPT2) and two contracted atomic natural orbital basis sets, S[6s4p3d1f]/O[5s3p2d1f] (ANO-L) and S[4s3p2d]/O[3s2p1d] (ANO-S), and the three states were considered to correspond to the observed X, B, and A states, respectively, in the previous experimental and theoretical studies. Based on the CASPT2/ANO-L adiabatic excitation energy calculations, the X, A, and B states of SO(2) (+) are assigned to 1 (2)A(1), 1 (2)B(2), and 1 (2)A(2), respectively, and our assignments of the A and B states are contrary to the previous assignments (A to (2)A(2) and B to (2)B(2)). The CASPT2/ANO-L energetic calculations also indicate that the 1 (2)A(1), 1 (2)B(2), and 1 (2)A(2) states are, respectively, the ground, first excited, and second excited states at the ground-state (1 (2)A(1)) geometry of the ion and at the geometry of the ground-state SO(2) molecule. Based on the CASPT2/ANO-L results for the geometries, we realize that the experimental geometries (determined by assuming the bond lengths to be the same as the neutral ground state of SO(2)) were not accurate. The CASPT2/ANO-S calculations for the potential energy curves as functions of the OSO angle confirm that the 1 (2)B(2) and 1 (2)A(2) states are the results of the Renner-Teller effect in the degenerate (2)Pi(g) state at the linear geometry, and it is clearly shown that the 1 (2)B(2) curve, as the lower component of the Renner splitting, lies below the 1 (2)A(2) curve. The UB3LYP/cc-pVTZ adiabatic excitation energy calculations support the assignments (A to (2)B(2) and B to (2)A(2)) based on the CASPT2/ANO-L calculations.     

Synthesis of (pentacarbonyl)tungstate(−1) and (pentacarbonyl)molybdate(−1) dinucleotides

New methods for preparation of metallo dinucleotides with transition metals directly bonded to phosphorus are presented. (Pentacarbonyl)tungstate(−1) and (pentacarbonyl)molybdate(−1) dimers are prepared by the reaction of dinucleotide-H-phosphonate with M(CO)₅(THF) (M = W, Mo). These syntheses can be completed in solution or on solid-phase.     

Facile syntheses of 1-deoxynojirimycin (DNJ) and 1-deoxymannojirimycin (DMJ)

1-Deoxynojirimycin (DNJ) and 1-deoxymannojirimycin (DMJ) were synthesized through a concise and practicable pathway. A strategy of using carbohydrate derivatives bearing two leaving groups in the preparation of azasugars by di-N-alkylation of amines was developed. The strategy involved the selective partial protection of dibromo alditols.     

Chromatographic properties and polarity evaluation of poly(1-trimethylsilyl-1-propyne) and poly(1-phenyl-1-propyne)

The chromatographic properties of poly(1-trimethylsilyl-1-propyne) (PTMSP) and poly(1-phenyl-1-propyne) (PPP) were studied by gas chromatography using packed columns. The selectivity and efficiency of columns packed with PTMSP and PPP were compared to the data obtained for columns with other known adsorbents and stationary phases. The McReynolds and Rohrschneider constants, on the basis of which the polarity of the new phases was evaluated, were calculated. The results of the investigation of chromatographic properties allow PTMSP to be brought in line with the polymeric adsorbents Porapak Q, Porapak QS, and Chromosorb 106, while PPP, with the methyphenylsilicon phases SE-52 and OV-3.     

DBU-promoted cyclization of ortho-(3-hydroxy-1-alkynyl)benzamide: synthesis of trans-3,4-dihydroisoquinolin-1(2H)-ones and (E)-4-(1-alkenyl)isoquinolin-1(2H)-ones

DBU-promoted cyclization of ortho-(3-hydroxy-1-alkynyl)benzamide is presented, providing an efficient method for the synthesis of trans-3,4-dihydroisoquinolin-1(2H)-ones and (E)-4-(1-alkenyl)isoquinolin-1(2H)-ones under mild conditions.     

Low-temperature magnetic behavior of perovskite compounds PbFe(1/2)Ta(1/2)O3 and PbFe(1/2)Nb(1/2)O3

The isostructural perovskite compounds PbFe(1/2)Ta(1/2)O3 and PbFe(1/2)Nb(1/2)O3 have been known for long time, and they are part of the important class of materials called multiferroic, where ferroelasticity, ferroelectricity, and ferromagnetism coexist. In the literature regarding PbFe(1/2)Ta(1/2)O3 and PbFe(1/2)Nb(1/2)O3, an "anomaly" of their low-temperature magnetic behavior has not always been reported. Moreover, both the origin of this behavior, and the cause for which it was not always observed, were never completely explained. In this paper, the magnetic behavior of the two compounds at low temperature has been extensively studied and explained as the occurring of a spin-glasslike transition.     

Fluorescence excitation spectra of the b (1)Pi(u), b(') (1)Sigma(u) (+), c(n) (1)Pi(u), and c(n) (') (1)Sigma(u) (+) states of N(2) in the 80-100 nm region

Fluorescence excitation spectra produced through photoexcitation of N(2) using synchrotron radiation in the spectral region between 80 and 100 nm have been studied. Two broadband detectors were employed to simultaneously monitor fluorescence in the 115-320 nm and 300-700 nm regions, respectively. The peaks in the vacuum ultraviolet fluorescence excitation spectra are found to correspond to excitation of absorption transitions from the ground electronic state to the b (1)Pi(u), b(') (1)Sigma(u) (+), c(n) (1)Pi(u) (with n=4-8), c(n) (') (1)Sigma(u) (+) (with n=5-9), and c(4) (')(v('))(1)Sigma(u) (+) (with v(')=0-8) states of N(2). The relative fluorescence production cross sections for the observed peaks are determined. No fluorescence has been produced through excitation of the most dominating absorption features of the b-X transition except for the (1,0), (5,0), (6,0), and (7,0) bands, in excellent agreement with recent lifetime measurements and theoretical calculations. Fluorescence peaks, which correlate with the long vibrational progressions of the c(4) (') (1)Sigma(u) (+) (with v(')=0-8) and the b(') (1)Sigma(u) (+) (with v(') up to 19), have been observed. The present results provide important information for further unraveling of complicated and intriguing interactions among the excited electronic states of N(2). Furthermore, solar photon excitation of N(2) leading to the production of c(4) (')(0) may provide useful data required for evaluating and analyzing dayglow models relevant to the interpretation of c(4) (')(0) in the atmospheres of Earth, Jupiter, Saturn, Titan, and Triton.     

(He 1) photoelectron spectra of vinyl- and (1-dimethylaminovinyl)pyridines

The (He 1) photoelectron spectra of -, -, -vinyl, -, -, and -(1-dimethylvinyl)-pyridines, 1-dimethyl- and 1-diethylaminostyrenes were obtained and interpreted within the framework of the molecular orbital perturbation theory. In both pyridine derivative series, there is a regular increase in the ionization energy of the 1a ₂, C=C and n_en orbitals and decrease in the ionization energy of the 2b₁ orbitals in the order < < (inversion of orbitals 1a ₂ and 2b₁ is found for -vinylpyridine). The splitting of the energy levels of the heterocycle in dimethylaminovinylpyridines is less than in the corresponding vinyl derivatives, which indicates a weakening of the interaction between the aromatic (or heteroaromatic) ring and the enamine fragment extruding from the ring plane. The ionization energy of the unshared electron pair of the nitrogen atom of the pyridine ring for all the compounds except for -(1-dimethylaminovinyl)pyridine (which displays an ortho effect) is close to that for pyridine. The photoelectron spectral data are compared with the MO energies calculated by the MINDO/3 method.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 103–108, January, 1985.     

The photodissociation reaction dynamics of CF(3)I at 304 nm ((3)Q(0+), (1)Q(1)<--(3)Q(0+), and (3)Q(1))

The photodissociation of CF(3)I at 304 nm has been studied using long time-delayed core-sampling photofragment translational spectroscopy. Due to its capability of detecting the kinetic energy distribution of iodine fragments with high resolution, it is able to directly assign the vibrational state distribution of CF(3) fragments. The vibrational state distributions of CF(3) fragments in the I(*)((2)P(12)) channel, i.e., (3)Q(0+) state, have a propensity of the nu(2) (') umbrella mode with a maximum distribution at the vibrational ground state. For the I((2)P(32)) channel, i.e., (1)Q(1)<--(3)Q(0+), the excitation of the nu(2) (') umbrella mode accounts for the majority of the vibrational excitation of the CF(3) fragments. The 1 nu(1) (') (symmetric CF stretch) +nnu(2) (') combination modes, which are associated with the major progression of the nu(2) (') umbrella mode, are observed for the photodissociation of CF(3)I at the I channel, i.e., (3)Q(1) state. The bond dissociation energy of the CI bond of CF(3)I is determined to be D(0)(CF(3)-I)相似文献   

Interaction between chicken protein tyrosine phosphatase 1 (CPTP1)-like rat protein phosphatase 1 (PTP1) and p60(v-src) in v-src-transformed Rat-1 fibroblasts

CPTP1 is a nontransmembrane chicken protein tyrosine phosphatase having 92% sequence homology to the corresponding 321 amino acids of human protein tyrosine phosphatase 1B (HPTP1B). Using anti-CPTP1 antibody, we identified CPTP1-like rat PTP1 of 51 kDa in Rat-1 and v-src-transformed Rat-1 fibroblasts. Here we show that CPTP1-like rat PTP1 binds to p60(v-src) in vivo and CPTP1 also can associate with p60(v-src) in cell lysate of v-src- transformed Rat-1 fibroblasts. Interaction between HPTP1B-type PTPs, CPTP1-like rat PTP1 and CPTP1, and p60(v-src) was reduced by vanadate treatment for 13 h due to down regulation of the protein level of p60(v-src) in vivo. Interestingly, CPTP1-like rat PTP1 was coimmunoprecipitated with a 70-kDa protein which has a possibility to be tyrosine- phosphorylated by p60(v-src) in v-src-transformed Rat-1 fibroblasts. These results suggest that HPTP1B-type PTPs may play an important role in p60(src) dependent signal pathway in eucaryotic cells.     

High resolution vacuum ultraviolet emission spectrum of D(2) from 78 to 103 nm: The D (1)Pi(u)-->X (1)Sigma(g) (+) and D(') (1)Pi(u) (-)-->X (1)Sigma(g) (+) band systems

The emission spectrum of the D(2) molecule has been studied at high resolution in the vacuum ultraviolet region 78.5-102.7 nm. A detailed analysis of the two D (1)Pi(u)-->X (1)Sigma(g) (+) and D(') (1)Pi(u) (-)-->X (1)Sigma(g) (+) electronic band systems is reported. New and improved values of the level energies of the two upper states have been derived with the help of the program IDEN [V. I. Azarov, Phys. Scr. 44, 528 (1991); 48, 656 (1993)], originally developed for atomic spectral analysis. A detailed comparison is made between the observed energy levels and solutions of coupled equations using the newest ab initio potentials by Wolniewicz and co-workers [J. Chem. Phys. 103, 1792 (1995); 99, 1851 (1993); J. Mol. Spectros. 212, 208 (2002); 220, 45 (2003)] taking into account the nonadiabatic coupling terms for the D (1)Pi(u) state with the lowest electronic states B (1)Sigma(u) (+), C (1)Pi(u), and B(') (1)Sigma(u) (+). A satisfactory agreement has been found for most of the level energies belonging to the D and D(') states. The remaining differences between observation and theory are probably due to nonadiabatic couplings with other higher electronic states which were neglected in the calculations.     

Metallation of poly(1-trimethylsilyl-1-prop-1-yne) and poly(vinyltrimethylsilane) with superbases

The pathway and degree of metallation of polymers were studied depending on the the conditions (temperature, concentration, nature, and component ratio) of metallation of poly(1-trimethylsilylprop-1-yne) (PTMSP) and poly(vinyltrimethylsilane) (PVTMS) by superbases, viz., BuⁿLi and Bu^sLi, in combination with potassium tert-pentyl oxide (Pe^tOK). For the BuⁿLi—Pe^tOK system (1 : 3), the yield of modified PTMSP reached 90%. In the case of PTMSP, only the Me groups at the double bonds and at the Si atoms undergo metallation, whereas only the Me groups at the Si atoms are metallated in PVTMS. The kinetics of metallation with the BuⁿLi—Pe^tOK system was studied.     

Synthesis of 1-(alkylamino)- and 1-(dialkylamino)benzimidazoline-2-thiones

Unlike 1-aminobenzimidazoles, 1-alkylaminobenzimidazoles are thiolated on fusing with sulfur without elimination of theN-amino group, yielding the previously unknown 1-(alkylamino)benzimidazoline-2-thiones. These compounds can be more conveniently obtained on a preparative scale by thiolation of 1-alkylacetamidobenzimidazoles with subsequent hydrolytic elimination of the acetyl group. When 1-(dialkylamino)benzimidazoles are fused with sulfur, they are converted into 1-(dialkylamino)benzimidazoline-2-thiones. By alkylation of 1-(methylamino)- and 1-(diethylamino)benzimidazoline-2-thiones with methyl iodide in alkaline media the corresponding 2-(methylthio)benzimidazoles were prepared.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2231–2235, November, 1995.The authors are grateful to the Contest Center of Basic Natural Science at St. Petersburg University for financial support of this study.     

Inhibition effects of gangliosides G(M1), G(D1a) and G(T1b) on base-catalyzed isomerization of prostaglandin A(2)

Micellar inhibition effect of gangliosides on a degradation of drug was investigated, where ganglioside G(M1) (GM1), G(D1a) (GD1a) and G(T1b) (GTlb) whose sialic acid residue is one, two and three, respectively, were used. The base-catalyzed isomerization of prostaglandin A(2) (PGA(2)) to prostaglandin B(2) (PGB(2)) was chosen as a model experiment. The rate for the isomerization of PGA(2) was determined by measuring the concentration of PGA(2) (and PGB(2)) with a high-performance liquid chromatography. Gangliosides micelles inhibited the isomerization of PGA(2). The inhibition effect of GT1b micelles was larger than that of GD1a micelles. This result would be due to the larger absolute value of surface potential of GT1b micelles, which brings about a larger electrostatic repulsion between micellar surface and OH(-). The terminal sialic acid residue of ganglioside was effective to inhibit the isomerization of PGA(2). GM1 micelles without terminal sialic acid residue but with large aggregation number exhibited a superior steric shielding effect rather than an electrostatically repulsive effect. The inhibition effect of GM1 micelles was enhanced by the mixed micellization with the other ganglioside with a terminal sialic acid residue. GM1-GD1a or GM1-GT1b mixed micelles remarkably inhibited the isomerization of PGA(2). The physiological activity of PGs in the biological membranes containing gangliosides was also discussed.     

Cross-coupling reactions of (1-fluorovinyl)methydiphenylsilane(1) with aryl halides and aryl triflates

The cesium fluoride (CsF)-assisted cross-coupling reaction of (1-fluorovinyl)methyldiphenylsilane (1) with aryl halides and aryl triflates was examined. The reaction with aryl iodides smoothly proceeded to afford the corresponding (1-fluorovinyl)arenes in the presence of a catalytic amount of CuI and Pd(PPh(3))(4) in aprotic polar solvents such as DMF, DMI, DMA, and NMP in good yields. A variety of functional groups (nitro, ester, ketone, and ether) on the aromatic rings can be tolerated under these mild conditions. Aryl iodides are superior to aryl bromides as the coupling reaction partner. The cross-coupling reaction of 1 with aryl triflates instead of aryl halides was also accomplished in the presence of tetrabutylammonium iodide (n-Bu(4)NI) as the additive under similar conditions.     

Synthesis of S-(carboran-1-yl)thiophosphates and S-(carboran-1-yl)-thiophosphonates

Conclusions New S-(carboran-1-yl)thiophosphates and S(carboran-1-yl)thiophosphonates were obtained by the reaction of derivatives of lithiumcarboranes with bis(dialkoxythiophosphoryl)disulfides or halo derivatives of pentavalent phosphorus.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 194–197, January, 1989.     

The behavior of 1-(5-oxazolyl)-1-alkylidenes and 1-(5-isoxazolyl)-1-alkylidenes

Capture, rearrangement and/or fragmentation of 1-(5-oxazolyl)-1-alkylidenes and 1-(5-isoxazolyl)-1-alkylidenes are described.     

Enzymatic synthesis of (R) and (S) 1-deuterohexanol

This paper describes practical enzymatic procedures for the synthesis of (R) and (S) 1-deuterohexanol, a useful building block for chiral poly isocyanated liquid crystals. Alcohol dehydrogenases from horse liver and Pseudomonas catalyzed the reduction of hexanal with deuterated NAD (NADD) resulting in 50% and 89% yields of (R) and (S) 1-deuterohexanol, respectively. The deuterated cofactor was regenerated in situ by alcohol dehydrogenase catalyzed oxidation of ethanol-d6 or 2-propanol-d8. The (S) alcohol was also synthesized by the horse liver alcohol dehydrogenase reduction of 1-deuterohexanal, which was prepared chemically from hexanal. The yields of the reaction were greatly increased by the use of a biphasic system or with the immobilized enzyme in anhydrous organic solvents. Horse liver alcohol dehydrogenase was stabilized by immobilization on PAN or noncovalent entrapment on XAD resin.     

13C-labeled platinum(IV)-carbohydrate complexes: structure determination based on (1)H-(1)H, (13)C-(1)H, and (13)C-(13)C spin-spin coupling constants

The reaction of D-mannose and D-allose with [PtMe(3)(Me(2)CO)(3)]BF(4) 1 in acetone affords complexes [PtMe(3)L]BF(4) 5 and 6 (5, L = alpha-D-mannofuranose; 6, L = beta-D-allofuranose). The coordination mode and conformation of the carbohydrate ligands in 5 and 6 in acetone-d(6) have been determined from an analysis of J(HH), J(CH), and J(CC) in complexes formed using site-specific (13)C-labeled D-mannose and D-allose. These coupling data are compared to those measured in (13)C-labeled complex [PtMe(3)L]BF(4) 2 (L = 1, 2-O-isopropylidene-alpha-D-glucofuranose) and 1, 2-O-isopropylidene-alpha-D-glucofuranose 3, whose solid-state structures are known, and in (13)C-labeled 1,2;5, 6-di-O-isopropylidene-alpha-D-glucofuranose 4. The preferred furanose ring conformations in 2 and 5 are very similar ((3)E/E(4) and E(4)/(o)E/E(1), respectively; eastern hemisphere of the pseudorotational itinerary), with platinum coordination involving O3, O5, and O6 of the saccharide. In contrast, the furanose ring of 6 prefers an (4)E/E(o)/(1)E geometry (western hemisphere of the pseudorotational itinerary) resulting from altered complexation involving O1, O5, and O6. Couplings within the exocyclic fragments of 2, 5, and 6 also support the existence of two different platinum coordination modes. In addition to establishing the structures and conformations of 2, 5, and 6 in solution, one-, two-, and three-bond J(CH) and J(CC) observed in these complexes provide new insights into the effect of structure and conformation on the magnitudes of these couplings in saccharides. Weak platinum(IV) complexation with the carbohydrate conformationally restricts the furanose and exocyclic fragment without introducing undesirable structural strain, thereby allowing more reliable correlations between structure and coupling magnitude.