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11.
Fabian Gerson Georg Gescheidt Reinhart Mckel Alexander Aumüller Peter Erk Siegfried Hünig 《Helvetica chimica acta》1988,71(7):1665-1672
The radical anions of 12 N,N′-dicyanoquinone diimines, a new class of electron acceptors, hace been characterized by their hyperfine data with the use of ESR and ENDOR spectroscopy. The largest coupling constant (0.30–0.45 mT), due to the two 14N nuclei in the exocyclic positions, gives rise to a conspicuous broadening of the peripheral ESR lines by an incomplete averaging of the hyperfine anisotropy. The most plausible interpretation of the experimental results for the radical anions of N,N′-dicyano- 1,4-benzoquinone diimine ( 1 ) and N,N′-Dicyano-9,10-anthraquinone diimine ( 9 ) is in terms of both ‘syn’- and ‘anti’-configurations contributing to the ESR and ENDOR spectra and having equal proton- and 14N-coupling constants. The π-spin distribution in the radical anions of N,N′-dicyanoquinone diimines is compared with those in the analogous ions of tetracyanoquinodimethanes and quinones. 相似文献
12.
Cong Zhang Christian Ludin Marcel K. Eberle Helen Stoeckli-Evans Reinhart Keese 《Helvetica chimica acta》1998,81(1):174-181
(S)-5,5,5,5′,5′,5′-Hexafluoroleucine ((S)- 13 ) of 81 % ee is prepared from hexafluoroacetone ( l ) and ethyl bromopyruvate (= ethyl 2-oxopropanoate) in 7 steps with an overall yield of 18% (Schemes 1 and 2). Key step in this sequence is the highly enantioselective reduction of the carbonyl group in α-keto ester 4 either by bakers' yeast (91 % ee) or by ‘catecholborane’ 6 utilizing an oxazaborolidine catalyst, yielding hydroxy ester (R)- 5 with 99% ee. The absolute configuration was determined by X-ray analysis of the HCl adduct (S,R)- 9b of (2S)-N-[(R)- l-phenylethyl]-5,5,5,5′,5′,5′-hexafluoroleucine ethyl ester. 相似文献
13.
Jan Brunvoll Rgine Guidetti-Grept Istvan Hargittai Reinhart Keese 《Helvetica chimica acta》1993,76(8):2838-2846
The efficient synthesis of all-cis-[5.5.5.5]fenestrane ( 2 ) from the readily available intermediate 3 allowed the electron-diffraction analysis of 2 . This structure analysis revealed long C? C bonds in the central C(C)4 fragment and a twist-envelope conformation for the four cyclopentane substructures. The four bridgehead H-atoms are in a synclinal rather than an ecliptic position with an approximate D2 symmetry of 2 . Planarizing distortions are evident from the opposite bond angles at the central C-atom being 116.2 ± 0.5° with the remaining four being 103.7 ± 0.2°. 相似文献
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Summary The SCF method is applied to determine the (gas phase) structure of [(CF3)2PN]2NVCl2, which agrees with the solid-state X-ray structure within typical errors of 2 pm and 2° in bond distances and angles. The electronic structure of atoms forming the ring is best described in terms of divalent N– and tetravlent P+ with appreciable declocalization of nitrogen lone pairs into low-lying empty orbitals of neighbouring atoms P and V. No evidence for aromaticity of the ring system is found. 相似文献
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Intramolecular arene-olefin photoreaction of methyl-6-methyl-2-phenylhept-5-enoate (9a) leads to the tetracyclic product 10a, from which the fenestra-dienone, 2, has been obtained. Mechanistic aspects of the photoreaction are discussed. 相似文献
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Electrochemical Formation of Δ1,2-Norbornene The electrochemical reduction of 1,2-dihalogen norbornanes in tetrahydrofuran/furan leads to a mixture of two isomeric cycloadducts 6 and 7. The ratio of these adducts corresponds to those which have been found in reductive bisdehalogenation of 1 and 2 by butyllithium. 相似文献
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