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91.
An enantioselective first total syntheis of amphidinolide T1 (1) is described. Amphidinolide T1 (1), a 19-membered macrolide isolated from Amphidinium sp., has shown potent antitumor properties against a variety of NCI tumor cell lines. The synthesis is convergent and involves the assembly of C1-C10 segment 2 and C11-C21 segment 3 by an oxocarbenium ion-mediated alkylation and Yamaguchi macrolactonization sequence. The synthesis of fragment 2 involves an efficient cross metathesis and hydrogenation sequence between the terminal olefins of 5 and 6 to form the C4-C5 carbon-carbon bond. Enol ether 4 is designed to be the surrogate of fragment 3 where the sensitive C16-exo-methylene and the C13-hydroxyl group were protected as the bromoether derivative during the Lewis acid-catalyzed alkylation process. Both stereocenters in fragment 5 as well as the C2 and C3 stereocenters in fragment 4 are accessed by a highly diastereoselective ester-derived titanium enolate-mediated syn-aldol reaction. The bromoether derivative 24 was unraveled at the final stage of the synthesis, providing (+)-amphidinolide T1. 相似文献
92.
[reaction: see text] (-)-Doliculide, a potent antitumor agent, is synthesized stereoselectively in a convergent manner. The key strategy involves a stereoselective synthesis of the polyketide unit and synthesis of the D-tyrosine derivative, followed by assembly of the fragments by an esterification and cycloamidation reaction sequence. The synthesis of the polyketide fragment was achieved by an iterative asymmetric synthesis to install stereoselectively both 1,3-dimethyl groups and the 1,3-diol unit by utilizing asymmetric cyclopropanations and Sharpless asymmetric epoxidations as the key steps. 相似文献
93.
Piperine, an alkaloid derived from the fruits of Piper nigrum, has been tested as an extracting bioreagent for gold. It has been observed that piperine as well as the fruits of Piper nigrum itself can act as an efficient exchanger for gold both in trace and macro scale. The accumulation of gold by these bioreagents
is highly pH dependent. 相似文献
94.
Premamoy Ghosh Samir Biswas Utpal Niyogi 《Journal of polymer science. Part A, Polymer chemistry》1986,24(5):1053-1063
Photopolymerization of methyl methacrylate (MMA) in visible light was studied at 40°C using Rhodamine 6G—Benzoyl peroxide combination as photoinitiator. The photopolymerization proceeds by a free radical mechanism and the radical generation process occurs by an initial complexation reaction between the initiator components. Kinetic data indicated a lower-order dependence of Rp on initiator concentrations (initiator exponent < 0.5). Initiator-dependent chain termination was significant along with the bimolecular mode of chain termination. 相似文献
95.
Novel bilirubin analogues with dipyrrinones conjoined to an acetylene rather than a methylene group were synthesized and examined spectroscopically. Despite the increased separation of the dipyrrinones forced by replacing a -CH(2)- by a -C(triple bond)C- unit, molecular dynamics calculations show that, like bilirubin, they may still engage in intramolecular hydrogen bonding to carboxylic acid groups when the propionic acid chains are slightly lengthened, e.g., butanoic acids. Unlike bilirubin, however, which is bent in the middle and has a ridge-tile shape, the acetylene orients the attached dipyrrinones along a linear path, and intramolecular hydrogen bonding preserves a twisted linear molecular shape. The extended planes of the dipyrrinones intersect along the -C(triple bond)C- axis at an angle of 136 degrees for the conformation stabilized by intramolecular hydrogen bonding in the bis-butyric acid rubin (1b). With shorter acid chains (propionic), only one CO(2)H can engage an opposing dipyrrinone in intramolecular hydrogen bonding, and in this energy-minimum conformation of the linear pigment 1a, the intersection of the extended planes of the dipyrrinones has an angle of 171 degrees. Spectroscopic evidence for such linearized and twisted structures was found in the pigments' NMR spectral data and their exciton UV-vis and induced circular dichroism spectra. 相似文献
96.
Summary [NiL2X2] (L =N,N-dimethyl-1,2-ethanediamine; X = Cl–, CF3CO
2
–
, CC13CO
2
–
and CBr3CO
2
–
), [NiL2C2O4] · H2O and [NiL2X2] · 2 H2O (X = Br–, 0.5 SO
4
2–
and 0.5 SeO
4
–
) have been synthesised and their thermal studies carried out. Thermally induced phase transition phenomena are noticed in [NiL2X2] (X = CF3CO
2
–
and CCl3CO
2
–
) and their probable mechanisms are described. [NiL2X2] (X = Br–, 0.5 SO
4
2–
and 0.5 SeO
4
2–
) and [NiLX2] (X = Cl–, 0.5 C2O
4
2–
and 0.5 SO
4
2–
) have been prepared by solid state pyrolysis from the respective parent diamine complexes. [NiL2X2] have been made in solid state by temperature arrest technique from [NiL2(CX3CO2)2] (X = Cl– and Br–). 相似文献
97.
Noorjahan Begum Amarash C. Ghosh Shariff E. Kabir Md. Arzu Miah G.M. Golzar Hossain 《Polyhedron》2005,24(18):3074-3081
Four triosmium carbonyl clusters bearing terminal pyrazines, bridging hydroxy and methoxycarbonyl ligands of general formula [Os3(CO)9(μ-OH)(μ-OMeCO)L] (1, L = pyrazine; 2, L = 2-methylpyrazine; 3, L = 2,3-dimethylpyrazine; 4, L = 2,3,5-trimethylpyrazine) were synthesized by the reactions of [Os3(CO)12] with the corresponding pyrazine derivatives and water in the presence of a methanolic solution of Me3NO in moderate yields. Compounds [Os3(CO)9(μ-OH)(μ-OMeCO)L] react with a series of two electron donor ligands, L′ at ambient temperature to give [Os3(CO)9(μ-OH)(μ-OMeCO)L′] (5, L′ = PPh3; 6, L′ = P(OMe)3; 7, L′ = tBuNC; 8, L′ = C5H5N) in good yields by the displacement of the pyrazine ligands. This implies that the pyrazine ligands in 1–4 are relatively labile. Compounds 2, 3, 4, and 8 were characterized by single crystal X-ray diffraction analyses. All the four compounds possess two metal–metal bonds and a non-bonded separation of two osmium atoms defined by Os(1)Os(3), which are simultaneously bridged by OH and MeOCO ligands and a heterocyclic ligand is terminally coordinated to one of the two non-bonded osmium atoms. 相似文献
98.
Archika?C.?Barve Smita?Ghosh Anupa?A.?Kumbhar Avinash?S.?KumbharEmail author Vedavati?G.?Puranik 《Transition Metal Chemistry》2005,30(3):312-316
The DNA binding characteristics of mixed ligand complexes of the type [Co(en)2(L)]Br3 where en = N,N′-ethylenediamine and L = 1,10-phenanthroline (phen), 2,2′-bipyridine (bpy), 1,10-phenanthroline-5,6-dione (phendione), dipyrido[3,2-a:2′,3′-c]phenazine (dppz) have been investigated by absorption titration, competitive binding fluorescence spectroscopy and viscosity measurements. The order of intercalative ability of the coordinated ligands is dppz > phen > phendione > bpy in this series of complexes. 相似文献
99.
Samanta S Ghosh D Mukhopadhyay S Endo A Weakley TJ Chaudhury M 《Inorganic chemistry》2003,42(5):1508-1517
The tridentate dithiocarbazate-based Schiff base ligands H(2)L (S-methyl-3-((5-R-2-hydroxyphenyl)methyl)dithiocarbazate, R = NO(2), L = L(2); R = Br, L = L(3)) react with [VO(acac)(2)] in the presence of imidazole derivatives as coligands to form oxovanadium(IV) and cis-dioxovanadium(V) complexes. With benzimidazole and N-methylimidazole, the products are oxovanadium(IV) complexes, viz. [VOL(3)(BzIm)].0.5CH(3)CN (1a) and [VOL(N-MeIm)(2)] (L = L(3), 1b; L = L(2), 1c), respectively. In both 1a,b, the O and S donor atoms of the tridentate ligand are cis to the terminal oxo group (in the "equatorial" plane) and mutually trans, but the N donor atom is respectively cis and trans to the oxo atom, as revealed from X-ray crystallography. When imidazole or 4-methylimidazole is used as the ancillary ligand, the products obtained are water-soluble cis-dioxovanadium(V) complexes [VO(2)L(R'-ImH)] (L = L(3) and L(2), R' = H and Me, 2a-d). These compounds have zigzag chain structures in the solid state as confirmed by X-ray crystallographic investigations of 2a,d, involving an alternating array of LVO(2)(-) species and the imidazolium counterions held together by Coulombic interactions and strong hydrogen bonding. Complexes 2a-d are stable in water or methanol. In aprotic solvents, viz. CH(3)CN, DMF, or DMSO, however, they undergo photochemical transformation when exposed to visible light. The putative product is a mixed-oxidation divanadium(IV/V) species obtained by photoinduced reduction as established by EPR, electronic spectroscopy, and dynamic (1)H NMR experiments. 相似文献
100.
Kallol K. Ghosh Pokhraj Sharma Samiksha Taramkar Santosh Kumar Sar 《Reaction Kinetics and Catalysis Letters》2004,81(1):161-168
The acid catalyzed hydrolysis of two N-substituted hydroxamic acids (C6H5CON(OH)R, R = C6H5 (PBHA), R = C6H5CH2(BBHA)) in mixed systems containing -cyclodextrin (—CD) and a surfactant (sodium dodecyl sulfate, SDS) has been studied. The reactions are inhibited by —CD. The inhibition is attributed to the formation of inclusion complex and competition between the micellization and complexation processes.This revised version was published online in December 2005 with corrections to the Cover Date. 相似文献