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121.
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(+)-4-epi-Gabosine A 1 and (−)-gabosine A 2 have been synthesized starting from methyl α,d-glucopyranoside and methyl α,d-mannopyranoside, respectively, by utilizing Pd(0) catalyzed Stille coupling as the key step. On the other hand, syntheses of (+)-4-epi-gabosine E 3 and (−)-gabosine E 4 have been accomplished from methyl α,d-glucopyranoside and from methyl α,d-mannopyranoside, respectively, by utilizing DMAP catalyzed Morita-Baylis-Hillman reaction as the key step. Presence of acetyl group at C-6 position of sugar derived cyclic enone prevented the aromatization of MBH adduct. A plausible mechanism is also described. 相似文献
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Stephen E Huang D Shaw JL Blake AJ Collison D Davies ES Edge R Howard JA McInnes EJ Wilson C Wolowska J McMaster J Schröder M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(37):10246-10258
The NiII complexes [Ni([9]aneNS2‐CH3)2]2+ ([9]aneNS2‐CH3=N‐methyl‐1‐aza‐4,7‐dithiacyclononane), [Ni(bis[9]aneNS2‐C2H4)]2+ (bis[9]aneNS2‐C2H4=1,2‐bis‐(1‐aza‐4,7‐dithiacyclononylethane) and [Ni([9]aneS3)2]2+ ([9]aneS3=1,4,7‐trithiacyclononane) have been prepared and can be electrochemically and chemically oxidized to give the formal NiIII products, which have been characterized by X‐ray crystallography, UV/Vis and multi‐frequency EPR spectroscopy. The single‐crystal X‐ray structure of [NiIII([9]aneNS2‐CH3)2](ClO4)6?(H5O2)3 reveals an octahedral co‐ordination at the Ni centre, while the crystal structure of [NiIII(bis[9]aneNS2‐C2H4)](ClO4)6?(H3O)3? 3H2O exhibits a more distorted co‐ordination. In the homoleptic analogue, [NiIII([9]aneS3)2](ClO4)3, structurally characterized at 30 K, the Ni? S distances [2.249(6), 2.251(5) and 2.437(2) Å] are consistent with a Jahn–Teller distorted octahedral stereochemistry. [Ni([9]aneNS2‐CH3)2](PF6)2 shows a one‐electron oxidation process in MeCN (0.2 M NBu4PF6, 293 K) at E1/2=+1.10 V versus Fc+/Fc assigned to a formal NiIII/NiII couple. [Ni(bis[9]aneNS2‐C2H4)](PF6)2 exhibits a one‐electron oxidation process at E1/2=+0.98 V and a reduction process at E1/2=?1.25 V assigned to NiII/NiIII and NiII/NiI couples, respectively. The multi‐frequency X‐, L‐, S‐, K‐band EPR spectra of the 3+ cations and their 86.2 % 61Ni‐enriched analogues were simulated. Treatment of the spin Hamiltonian parameters by perturbation theory reveals that the SOMO has 50.6 %, 42.8 % and 37.2 % Ni character in [Ni([9]aneNS2‐CH3)2]3+, [Ni(bis[9]aneNS2‐C2H4)]3+ and [Ni([9]aneS3)2]3+, respectively, consistent with DFT calculations, and reflecting delocalisation of charge onto the S‐thioether centres. EPR spectra for [61Ni([9]aneS3)2]3+ are consistent with a dynamic Jahn–Teller distortion in this compound. 相似文献
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The palladium-catalyzed, hydroxyl-directed cyclization reactions of 1,6-enynes provide a highly diastereoselective process for the syntheses of stereochemically defined cyclopentanes. Consistently high levels of cis-selectivity are possible using homopropargyl alcohols in contrast to the corresponding propargyl alcohols. Hydroborylative enyne cyclizations coupled with this directing group effect provide a useful method for the syntheses of multifaceted compounds bearing all carbon quaternary centers. 相似文献
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The development of an innovative method to access enantiopure 2,4-disubstituted 6-hydroxy-1,6-dihydro-2H-pyridin-3-ones starting from D-glucal via the aza-Achmatowicz transformation has been described. These highly functionalized pyridin-3-ones have been utilized for the synthesis of contiguously substituted pyridines through a rapid and efficient Et(3)N/Ac(2)O promoted cyclo-elimination, aromatization cascade, allowing the facile assembly of important pyridine-based building blocks like 2-substituted 3-acetoxy-4-iodopyridines and enantiopure 2-substituted 3-acetoxy-4-pyridinemethanols possessing benzylic stereogenic centers, whose synthesis otherwise would be tedious. The utilization of commercially available sugars as starting materials, mild reaction conditions, catalytic transfer hydrogen (CTH) of α-furfuryl azide derivatives, transfer of chiral aryl/alkyl methanols from enulosides to pyridin-3-ones and pyridines, high yields, and short reaction times are key features of this method. The utility of the method has been further exemplified by demonstrating the usage of the 2-substituted 3-acetoxy-4-iodopyridine for the construction of biologically significant molecules like 2,7-disubstituted furo[2,3-c]pyridines and 7,7'-disubstituted 2,2'-bifuro[2,3-c]pyridines. 相似文献
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Padhee S Hu Y Niu Y Bai G Wu H Costanza F West L Harrington L Shaw LN Cao C Cai J 《Chemical communications (Cambridge, England)》2011,47(34):9729-9731
We report a new class of peptide mimetics, α-AApeptides, that display broad-spectrum activity against both Gram-negative and Gram-positive bacteria and fungi. With non-hemolytic activity, resistance to protease hydrolysis, and easy sequence programmability, α-AApeptides may emerge as a novel class of antibiotics. 相似文献
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Guo J Baker GA Hillesheim PC Dai S Shaw RW Mahurin SM 《Physical chemistry chemical physics : PCCP》2011,13(27):12395-12398
In this work, we provide new experimental evidence for chain length-dependent self-aggregation in room temperature ionic liquids (RTILs) using fluorescence correlation spectroscopy (FCS). In studying a homologous series of N-alkyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide, [C(n)MPy][Tf(2)N] RTILs of varying alkyl chain length (n = 3, 4, 6, 8, and 10), biphasic rhodamine 6G solute diffusion dynamics were observed; both the fast and slow diffusion coefficients decreased with increasing alkyl chain length, with the relative contribution from slower diffusion increasing for longer-chain [C(n)MPy][Tf(2)N]. We propose that the biphasic diffusion dynamics originate from self-aggregation of the nonpolar alkyl chains in the cationic [C(n)MPy](+). 相似文献