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961.
Reaction of Os3(CO)10(NCMe)2 and 1,5-cyclooctadiene (C8H12) affords the diene complex Os3(CO)10(η4-C8H12) (1) with the two alkene moieties coordinated to an equatorial and an axial positions of one osmium atom. Thermolysis of 1 in refluxing n-hexane results in a vinylic C-H bond activation to form (μ-H)Os3(CO)9(μ,η4-C8H11) (2) in good isolated yield. The crystal structures of 1 and 2 have been established by an X-ray diffraction study. 相似文献
962.
Five new compounds, hibicuslide A (1), hibicuslide B (2), hibicuslide C (3), hibicutaiwanin (4), hibicusin (5), and fifty-one known compounds have been isolated from the stems of Hibiscus taiwanensis. The structures of these compounds were determined by spectroscopic and chemical transformation methods. Among them, mansonone H (19) and uncarinic acid A (30) inhibited HIV replication in H9 lymphocyte cells. The 9,9'-O-feruloyl-(-)-secoisolaricinresinol (12), myriceric acid C (29), and uncarinic acid A (30) showed cytotoxic activity against human lung carcinoma and breast carcinoma. 相似文献
963.
[reaction: see text] (-)-Sparteine-mediated asymmetric lithiation-substitution sequences of 2- and 3-substituted N-(Boc)-N-(p-methoxyphenyl) allylic amines with electrophiles have been investigated. Asymmetric lithiation-substitutions of N-(Boc)-N-(p-methoxyphenyl) allylic amines 11, 12, 13, 14, and 15 provide highly enantioenriched enecarbamates in good yields. Further transformations to give aldehydes, acids, ketones, and a Diels-Alder adduct are reported. The 1,4-addition products from reactions of the lithiated allylic amines from 14 and 15 with conjugated activated alkenes gives enecarbamates with two and three stereogenic centers in good yields with high diastereomeric and enantiomeric ratios. Synthetic transformation of these products by acid hydrolysis and subsequent cyclization provide stereoselective access to bicyclic compounds containing four and five stereogenic centers with high diastereoselectivity and enantioselectivity. It is suggested that allyllithium complexes generated by asymmetric deprotonation react with most electrophiles with inversion of configuration. 相似文献
964.
Liquid chromatographic comparisons for enantiomer resolution of α-amino acids and chiral primary amino compounds were made using chiral stationary phases (CSPs) prepared by covalently bonding (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid (18-C-6-TA) of the same chiral selector. The resolution of all α-amino acids on CSP 1 developed in our group was found to be better than that on CSP 2 reported by Machida et al. All α-amino acids examined in this study were well enantioseparated on CSP 1 (α=1.22–2.47), while four analytes were not resolved or all the other analytes were poorly resolved on CSP 2 than on CSP 1. However, in resolving the primary amino compounds without a carbonyl group, CSP 1 was comparable with CSP 2. Although (+)-18-C-6-TA of the same chiral selector was used to prepare CSP 1 and CSP 2, this study showed that different connecting methods for the CSPs might influence their ability to resolve the analytes depending on their structures related to the chiral recognition mechanism. 相似文献
965.
Reaction of 1,3,5-trimethyl-1,3,5-triazacyclohexane [(MeNCH2)3] with Os3(CO)12 in refluxing toluene results in C-H and C-N bond activation of the (MeNCH2)3 ligand to afford three amidino cluster complexes (μ-H)Os3(CO)10[μ,η2-CH(NMe)2] (1), (μ-H)Os3(CO)9[μ3,η2-CH(NMe)2] (2), and Os2(CO)6[μ,η2-CH(NMe)2]2 (3). The controlled experiments show that thermolysis of 1 yields 2, and heating 2 in the presence of (MeNCH2)3 ligand produces 3. The molecular structures of 1 and 3 have been determined by an X-ray diffraction study. 相似文献
966.
Kang SH Song JH Kang HK Kang JH Kim SJ Kang HW Lee YK Park DB 《Experimental & molecular medicine》2003,35(2):83-90
Arsenic trioxide (As(2)O(3)) has been found to be remarkably effective in the treatment of patients with acute promyelocytic leukemia (APL). Although evidences for the proapoptotic activity of As(2)O(3) have been suggested in leukemic and other solid cancer cells, the nature of intracellular mechanisms is far from clear. In the present study, we investigated As(2)O(3) affect on the stress-responsive signaling pathways and pretreatment with antioxidants using HepG2 cells. When treated with micromolar concentrations of As(2)O(3), HepG2 cells became highly apoptotic paralleled with activation of caspase-3 and members of mitogen-activated protein kinases (MAPKs) including extracellular signal-regulated kinase (ERK) and c-jun NH(2)-terminal kinase (JNK) but not p38 MAP kinase. However, inhibition of each kinase activity failed to inhibit apoptosis by As(2)O(3). Addition of n-acetyl cysteine (NAC) or diphenyleneiodonium (DPI) effectively protected cells from apoptosis and significantly lowered As(2)O(3)-induced activation of caspase-3. However, neither NAC nor DPI was able to effect ERK or JNK activation induced by As(2)O(3). Guanidinoethyldisulfide dihydrochloride (GED) and 2-ethyl-2-thiopseudourea (ETU), known inhibitors of the inducible nitric oxide synthase (iNOS), also suppressed the apoptotic activity of As(2)O(3). These results suggest that As2O3 induces caspase-mediated apoptosis involving a mechanism generating oxidative stress. However, activation of some stress-responsive signaling pathways by As(2)O(3) may not be the major determinant in the course of apoptotic processes. 相似文献
967.
Three new pregnane glycosides, cynatroside A ( 1 ), cynatroside B ( 2 ), and cynatroside C ( 3 ), isolated from the roots of Cynanchum atratum (Asclepiadaceae), were characterized as 7β‐{[O‐α‐L ‐cymaropyranosyl‐(1→4)‐O‐β‐D ‐digitoxopyranosyl‐(1→4)‐β‐D ‐oleandropyranosyl]oxy}‐3,4,4a,4b,5,6,7,8,10,10a‐decahydro‐6α‐hydroxy‐4b‐ methyl‐2‐(2‐methyl‐3‐furyl)phenanthren‐1(2H)‐one ( 1 ), 7β‐{[O‐β‐D ‐cymaropyranosyl‐(1→4)‐O‐α‐L ‐diginopyranosyl‐(1→4)‐β‐D ‐cymaropyranosyl]oxy}‐3,4,4a,4b,5,6,7,8,10,10a‐decahydro‐2,6α‐dihydroxy‐4b‐methyl‐2‐(2‐methyl‐3‐furyl)phenanthren‐1(2H)‐one ( 2 ), and 7β‐{[O‐α‐L ‐cymaropyranosyl‐(1→4)‐O‐β‐D ‐digitoxopyranosyl‐(1→4)‐β‐L ‐cymaropyranosyl]oxy}‐3,4,4a,4b,5,6,7,8,10,10a‐decahydro‐2,6α‐dihydroxy‐4b‐methyl‐2‐(2‐methyl‐3‐furyl)phenanthren‐1(2H)‐one ( 3 ), respectively. In addition, ten known constituents were identified, i.e., cynascyroside D ( 4 ), glaucoside C ( 5 ), glaucoside D ( 6 ), atratoside A ( 7 ), 2,4‐dihydroxyacetophenone ( 8 ), 4‐hydroxyacetophenone ( 9 ), syringic acid ( 10 ), azelaic acid ( 11 ), suberic acid ( 12 ), and succinic acid ( 13 ). Among these compounds, 1 – 4 significantly inhibit acetylcholinesterase activity. 相似文献
968.
Cyclization were occurred via the coupling reactions of some mercuric chloride derivatives of sydnone with LiPdCl3-CuCl2. A unique six-membered ring, 3,3′-ethylene-4,4′-bissydnone, was obtained by the cyclization reation of 1,2-di[3-(4-chloromercuric)sydnonyl]ethane. However, the seven-membered 3,3′-trimethylene-4,4′-bissydnone and 1,3-di[3-(4-chloro)sydnonyl]-propane were obtained from the corresponding mercuric chlroide of sydnone. Onyl substitution reaction took place when 4,4′-di[3-(4-chloromercuric)sydnonyl]biphenyl, 4,4′-di[3-(4-chloromercuric)sydnonyl]benzene, di(p-[3-(4-chloromercuric)sydnonyl]-phenyl}methane and, di(p-[3-(4-chloromercuric)sydnonyl]phenyl]ether were treated using the same process. 相似文献
969.
New AP Wolff JC Crabtree S Freitas do Santos L Okafo G Lee J Divan K 《Journal of chromatography. A》2001,913(1-2):205-208
We have recently investigated the biodegradation of a number of acidic aromatic compounds that give excellent chromatography using trifluoroacetic acid (TFA) based HPLC methods. Unfortunately HPLC methods using TFA are not usually compatible with detection by negative ion mass spectrometry as TFA suppresses ionisation of the analyte during the electrospray process. We present a preliminary investigation of the use of an anion-exchange micro-membrane suppressor to remove TFA on-line post column with the aim of improvement of mass spectral data using an aromatic acid as an example, Thus LC-MS using a TFA based HPLC method with negative ion mass spectral detection is shown to be possible with good sensitivity. 相似文献
970.
[reaction: see text] A new phosphine-imidazolium salt, L.HBr (1, L = (1-ethylenediphenylphosphino-3-(mesityl))imidazol-2-ylidene), has been prepared. A combination of 0.5 mol % of Pd(dba)(2) and 0.5 mol % of L.HBr in the presence of 2 equiv of Cs(2)CO(3) as base has proven to be highly efficient in the Heck coupling reactions of aryl bromides (from electron-deficient to electron-rich aryl bromides) with n-butyl acrylate. 相似文献