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941.
942.
Reaction of lithium enolates of simple ketones with (+/-)-phenyl vinyl sulfoxide has potential for the convergent construction of complex fused ring systems containing a bicyclo[n.2.0]alkan-1-ol. The formation of sulfinylbicyclo[4.2.0]octan-1-ols 1-3 from the lithium enolate of cyclohexanone with (+/-)-phenyl vinyl sulfoxide or (R)-(+)-p-tolyl vinyl sulfoxide 18 was used to probe the mode of this novel cyclization reaction. Using phenyl vinyl sulfoxide, variations in the reaction lighting and solvent were investigated, in conjunction with radical trapping (TEMPO) and isotope labeling (deuterium) experiments. Cyclization to form sulfinylbicyclooctanols 1-3 is likely to proceed via an intermediate that ring closes to the bicycloalkanol anion 11 and was presently favored by the use of solvents such as THF or DME. 相似文献
943.
Chatterjee B Noveron JC Resendiz MJ Liu J Yamamoto T Parker D Cinke M Nguyen CV Arif AM Stang PJ 《Journal of the American Chemical Society》2004,126(34):10645-10656
The syntheses, structures, and N2 adsorption properties of six new supramolecular metallacycles are reported. Flexible ditopic linkers, 1-4, with systematically varied lengths and conformational degrees of freedom were synthesized utilizing ester linkages. They were used in combination with (dppp)M(OTf)2, where M = Pt(II) and Pd(II), and cis-(Me3P)2Pt(OTf)2 to form flexible supramolecular metallacycles 5-10 in 88-98% isolated yields. Their structures were characterized via multinuclear NMR and X-ray crystallography. The metallacycles stack to form porous structures in the crystalline state. The pore dimensions depend on both the phosphorus ligands attached to the metals and the flexible linkers. Adsorption studies on the porous materials show that 5a, 6, 8, and 9 held 11.7, 16.5, 5.7, and 6.8 cm3/g STP of N2 at 77 K, respectively. A guest-exchange study with nitromethane and toluene reveals that the nanopore in 5 is flexible, a property which was transferred from the linker to the supramolecular structure in the solid state. 相似文献
944.
945.
[reaction: see text] A facile and efficient methodology of the synthesis of 6-(hydroxymethyl)purine derivatives (bases and nucleosides) was developed based on Pd-catalyzed cross-coupling reactions of 6-halopurines with acyloxymethylzinc iodides followed by deprotection. Several title compounds are inhibitors of adenosine deaminase and exert cytostatic activity. 相似文献
946.
Drew MG Hill C Hudson MJ Iveson PB Madic C Youngs TG 《Dalton transactions (Cambridge, England : 2003)》2004,(2):244-251
The extracting agent 2,6-bis(4,6-di-pivaloylamino-1,3,5-triazin-2-yl)-pyridine (L(5)) in n-octanol was found, in synergy with 2-bromodecanoic acid, to give D(Am)/D(Eu) separation factors (SFs) between 2.4 and 3.7 when used to extract the metal ions from 0.02-0.12 M HNO(3). Slightly higher SFs (4-6) were obtained in the absence of the synergist when the ligand was used to extract Am(III) and Eu(III) from 0.98 M HNO(3). In order to investigate the possible nature of the extracted species crystal structures of L(5) and the complex formed between Yb(III) with 2,6-bis(4,6-di-amino-1,3,5-triazin-2-yl)-pyridine (L(4)) were also determined. The structure of L(5) shows 3 methanol solvent molecules all of which form 2 or 3 hydrogen bonds with triazine nitrogen atoms, amide nitrogen or oxygen atoms, or pyridine nitrogen atoms. However, L(5) is relatively unstable in metal complexation reactions and loses amide groups to form the parent tetramine L(4). The crystal structure of Yb(L(4))(NO(3))(3) shows ytterbium in a 9-coordinate environment being bonded to three donor atoms of the ligand and three bidentate nitrate ions. The solvent extraction properties of L(4) and L(5) are far inferior to those found for the 2,6-bis-(1,2,4-triazin-3-yl)-pyridines (L(1)) which have SF values of ca. 140 and theoretical calculations have been made to compare the electronic properties of the ligands. The electronic charge distribution in L(4) and L(5) is similar to that found in other terdentate ligands such as terpyridine which have equally poor extraction properties and suggests that the unique properties of L(1) evolve from the presence of two adjacent nitrogen atoms in the triazine rings. 相似文献
947.
10,25-Di-tert-alkyl-14,21-dimethyl-3,6,14,21-tetraazatricyclo[21.3.1.18,12]octacosa-1(27),2,6,8,10,12(28),23,25-octaene-27,28-diol macrocycles form Ni(II) and Cu(II) complexes in which the metal cation and the sulfate anion are bound in separated sites in a zwitterionic form of the ligand. The nonyl-substituted macrocycle shows a higher affinity for SO(4)(2-) and a lower binding strength for Cu(2+) than open chain analogues, the pH-dependences for which fall in ranges which allow loading of CuSO(4) at pH approximately 4 and easy stripping to recycle the ligand. X-Ray structure determinations of the Cu(II) and Ni(II) sulfate complexes of the tert-butyl substituted ligand suggest that the de-tuning of M(2+)-binding results from a distortion from planarity of the "salen" N(2)O(2)(2-) donor set imposed by the incorporation of the hexamethylene strap in the ligand and reveal that the sulfate is bound as a hydrate in a 2:2:2:2, ligand-M(2+)-SO(4)(2-)-H(2)O, assembly. 相似文献
948.
949.
The asymmetric total synthesis of (-)-reveromycin A is described. The key steps involved a Lewis acid catalyzed inverse electron demand hetero-Diels-Alder reaction followed by hydroboration/oxidation to afford the spiroketal core 4 in a highly stereoselective manner and introduction of the C18 hemisuccinate by high-pressure acylation. 相似文献
950.
Asymmetric additions of alkyl radicals, generated from R3B, to chiral 2H-azirine-3-carboxylates offer a new entry to enantio-enriched aziridines, and proceed with high diastereoselectivity when using 8-phenylmenthol as chiral auxiliary. 相似文献