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Foltz C Stecker B Marconi G Bellemin-Laponnaz S Wadepohl H Gade LH 《Chemical communications (Cambridge, England)》2005,(40):5115-5117
Chiral C3-symmetric trisoxazolines are highly efficient stereodirecting ligands in enantioselective Cu(II) Lewis acid catalysis which is based on the concept of a stereoelectronic hemilability of the divalent copper; in direct comparison with the analogous bisoxazoline systems they are more efficient in the enantioselective alpha-amination as well as the enantioselective Mannich reaction of prochiral beta-ketoesters. 相似文献
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Foltz C Stecker B Marconi G Bellemin-Laponnaz S Wadepohl H Gade LH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(35):9912-9923
The underlying conceptual differences in exploiting two- and threefold rotational symmetry in the design of chiral ligands for asymmetric catalysis have been addressed in a comparative study of the catalytic performance of bisoxazoline (BOX) and tris(oxazolinyl)ethanes (trisox) containing copper(II) Lewis acid catalysts. The differences become apparent in constructing new catalysts by systematically "deforming" the stereodirecting ligand by inverting chiral centres or replacing chiral by achiral oxazolines. The catalytic alpha-amination of ethyl 2-methylacetoacetate with dibenzyl azodicaboxylate, which occurs with high enantioselectivity for both Ph(2)-BOX and Ph(3)-trisox copper catalysts, has been employed as the test reaction. In the trisox-copper complex [Cu(II)(iPr(3)-trisox)(kappa(2)-O,O'-MeCOCHCOOEt)](+)[BF(4)](-) (1), which was characterised by X-ray diffraction, two of the oxazoline groups are coordinated to the central copper atom, whilst the third oxazoline unit is dangling with the N-donor pointing away from the metal centre. A similar arrangement is found for the stereochemically "mixed" C(1)-trisox complex [Cu(II){(Ph(3)-trisox(R,S,S)}(kappa(2)-O,O'-MeCOCHCOOEt)(H(2)O)](+)[ClO(4)](-) (2), in which the phenyl substituents adopt a first coordination sphere meso arrangement. The almost identical selectivity of the Ph(3)-trisox(R,R,R)- and Ph(2)-BOX(R,R)-derived catalysts is as expected from the proposed model of the active catalyst based on a partially decoordinated podand. The behaviour of the "desymmetrised" trisox-Cu catalysts may be rationalised in terms of a general steady-state kinetic model for the three possible active bisoxazoline-copper species, which are expected to be in rapid exchange with each other in solution. This applies to both the trisox derivatives with stereochemically inverted and achiral oxazoline rings. The study underscores previous observations of superior performance of the catalysts bearing C(3)-chiral stereodirecting ligands as compared to systems of lower symmetry. 相似文献
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Tietze LF Stecker F Zinngrebe J Sommer KM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(34):8770-8776
An enantioselective total synthesis of vitamin E in which a novel palladium-catalyzed domino reaction was employed as the key step is described. This reaction allows the formation of the chiral chroman framework and the concurrent introduction of part of the side chain of vitamin E. The sequence comprises an enantioselective Wacker cyclization and a subsequent Heck reaction. Accordingly, reaction of alkenylphenol 12 with methyl vinyl ketone (13) in the presence of catalytic amounts of Pd(OTFA)(2) (TFA = trifluoroacetate), the enantiopure ligand (S,S)-Bn-BOXAX (8 b; Bn = benzyl, BOXAX = 2,2'-bis(oxazolyl)-1,1'-binaphthyl, and p-benzoquinone (9) as an oxidant gives access to chiral chroman 10 with an enantioselectivity of 97 % ee in 84 % yield. Chroman 10 is then converted into 24 by an aldol condensation reaction with (3R)-3,7-dimethyloctanal (11). Subsequent 1,2-addition of methyllithium, elimination of water, and hydrogenation yields vitamin E. 相似文献
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Listeners detected interaural differences of time (ITDs) or level (ILDs) carried by single 4000-Hz Gabor clicks (Gaussian-windowed tone bursts) and trains of 16 such clicks repeating at an interclick interval (ICI) of 2, 5, or 10 ms. In separate conditions, target interaural differences favored the right ear by a constant amount for all clicks (condition RR), attained their peak value at onset and diminished linearly to 0 at offset (condition R0), or grew linearly from 0 at onset to a peak value at offset (condition 0R). Threshold ITDs and ILDs were determined adaptively in separate experiments for each of these conditions and for single clicks. ITD thresholds were found to be lower for 16-click trains than for single clicks at 10-ms ICI, regardless of stimulus condition. At 2-ms ICI, thresholds in RR and R0 conditions were similar to single click thresholds at 2-ms ICI; thresholds in the 0R condition were significantly worse than for single clicks at 2-ms ICI, consistent with strong rate-dependent onset dominance in listeners' temporal weighting of ITD. ILD thresholds, in contrast, were predominantly unaffected by ICI, suggesting little or no onset dominance for ILD of high-rate stimuli. 相似文献
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Noncollinear difference frequency mixing of dye laser and Nd:YAG second harmonic (fundamental) radiation from a commercial
laser system is employed for the generation of 2.7–5.3 μm (1.6–1.7 μm) radiations in a flux-grown KTiOAsO1 crystal. The generated radiation is used to scan the methane absorption in the fundamental (v
3) and its first overtone (2v
3) band at pressure 90 torr in a laboratory made single pass gas cell of length 33 cm. 相似文献