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1.
《Journal of organometallic chemistry》2004,689(20):3232-3241
Cationic cycloaddition of cross-conjugated 3-ferrocenylmethylidene-2,4-dimethylpenta-1,4-diene to 1-ferrocenyl-2-isopropenyl-3,3-dimethylallylium tetrafluoroborate and its proton-catalyzed cyclodimerization result in diferrocenylbicyclo[3.3.1]nonene derivatives. The spatial structure of one of the reaction products, viz., ferroceno[4,5]-{9-ferrocenylmethylidene-1,3,3,8,10-pentamethyltricyclo[6.3.1.02,6]dodec-2(6)-ene}, was established based on the data from X-ray diffraction analysis. 相似文献
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Asymmetric Brønsted Base Catalyzed and Directed [3+2] Cycloaddition of 2‐Acyl Cycloheptatrienes with Azomethine Ylides
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Vibeke H. Lauridsen Lise Ibsen Jakob Blom Prof. Dr. Karl Anker Jørgensen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(10):3259-3263
Conjugated cyclic trienes have the potential for different types of cycloaddition reactions. In the present work, we will, in a novel asymmetric cycloaddition reaction, demonstrate that the organocatalytic reaction of 2‐acyl cycloheptatrienes with azomethine ylides proceeds as a [3+2] cycloaddition, which is in contrast to the Lewis acid‐catalyzed reaction, in which a [3+6] cycloaddition takes place. In the presence of a chiral organosuperbase, 2‐acyl cycloheptatrienes react in a highly enantioselective manner in the [3+2] cycloaddition with azomethine ylides, providing the 1,3‐dipolar cycloaddition product in high yields and up to 99 % ee. It is also shown that the diene formed by the reaction can undergo stereoselective dihydroxylation, bromination, and cycloaddition reactions. Finally, based on experimental observations, some mechanistic considerations are discussed. 相似文献
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1-Cyclohepta-2,4,6-trienyl-selanes Se(C(7)H(7))(2) (2c), R--Se--C(7)H(7) with R = Bu, (t)Bu, Ph, 4-F--C(6)H(4) (12a,b,c,d) were prepared by the reaction of the corresponding silanes, Si(SeMe(3))(2) and R--Se--SiMe(3), respectively, with tropylium bromide C(7)H(7)Br. In spite of the low stability of the selanes even in dilute solutions and at low temperature, they could be characterised by their (1)H, (13)C and (77)Se NMR parameters. Coupling constants (1)J((77)Se,(13)C) were measured and calculated by DFT methods at the B3LYP/6-311+G(d,p) level of theory. The comparison of experimental and calculated coupling constants (1)J((77)Se,(13)C) included numerous selenium carbon compounds with largely different Se--C bonds, revealing a satisfactory agreement. Both the spin-dipole (SD) and the paramagnetic spin-orbital (PSO) terms contributed significantly to the spin-spin coupling interaction, in addition to the Fermi contact (FC) term. 相似文献
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Conversion of acyclic allenynes to polycyclic compounds using consecutive transition metal catalyzed carbon-carbon bond forming reactions in a single chemical operation is described. Reaction of an allenyne with a Rh(I) catalyst affords a cross-conjugated triene via a formal Alder-ene reaction. The triene then participates in a Rh(I)-catalyzed intramolecular [4+2] cycloaddition reaction to generate a new conjugated diene. An external dienophile is added to this diene which then undergoes a second [4+2] cycloaddition reaction to afford a complex polycyclic ring system. This reaction sequence demonstrates the synthetic potential of allenynes and cross conjugated trienes and highlights the rapid increases in molecular complexity that are possible by one-pot sequential transition metal catalyzed carbon-carbon bond forming reactions. 相似文献
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Masataka Watanabe Taisuke Matsumoto Shuntaro Mataka Thies Thiemann 《Central European Journal of Chemistry》2006,4(3):375-402
17-Thienyl-and 17-benzo[b]thienyl-3-hydroxyestra-1,3,5(10),16-tetraenes were synthesized by either sequential or one-pot Suzuki cross-coupling and
Wittig olefination reactions. At 160 °C, heteroaryl substituted steroids were observed to undergo thermal intramolecular cyclization
to produce E-ring heteroareno-annelated estranes. 相似文献
7.
A Versatile and Stereocontrolled Total Synthesis of Dihydroxylated Docosatrienes Containing a Conjugated E,E,Z‐Triene
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Dr. Gandrath Dayaker Dr. Thierry Durand Dr. Laurence Balas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(10):2879-2887
A versatile strategy featuring a Colvin rearrangement, hydrozirconation, a Sonogashira cross‐coupling reaction and a Z‐selective Wittig olefination, was successfully developed for the construction of a conjugated E,E,Z‐triene subunit, flanked on both sides by two Z‐allylic hydroxyl groups. This chemical pattern is found in many endogenous lipid metabolites such as maresin 1 (MaR1), neuroprotectin D1 (NPD1), and its aspirin triggered‐isomer AT‐NPD1, which not only counter‐regulate inflammation but also actively orchestrate (at nanomolar doses) the resolution and termination program of acute inflammation while promoting wound healing, return to homeostasis and neuroprotection. Unlike previous approaches, the advantages of the present strategy are obvious, as it allows us to modify the nonpolar tail, the carboxylated head or both ends of the molecule without repeating the whole synthetic sequence (about 26–34 steps according to the literature). Thus, the first total syntheses of NPD1 methyl ester epimer (which can also be considered as an enantiomer of AT‐NPD1) and its n‐3 docosapentaenoic acid derived analogue were achieved from a highly functionalized and late advanced pivotal intermediate. This innovative route may be easily adapted to gain access to other dihydroxylated metabolites and analogues of polyunsaturated fatty acids containing a conjugated E,E,Z‐triene subunit. Different epimers/diastereoisomers may be obtained by purchasing the suitable optically pure (S)‐ and/or (R)‐1,2,4‐butanetriol(s) as a chiral pool for both stereogenic centers. 相似文献
8.
Wei Li Dr. Min Shi Prof. Dr. Yuxue Li Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(35):8852-8860
Diarylvinylidenecyclopropanes undergo a novel rearrangement in the presence of the Brønsted acid Tf2NH (Tf: trifluoromethanesulfonyl) to give the corresponding naphthalene derivatives in good to high yields upon heating, whereas in the presence of the Brønsted acid toluene‐4‐sulfonic acid (p‐TSA), the corresponding triene derivatives are afforded in moderate to good yields under mild conditions. Corresponding mechanistic studies on the basis of density functional theory (DFT) with the Gaussian03 program by using the B3LYP method have revealed that the pKa value of the Brønsted acid, as well as the entropy and solvent effects, plays a significant role in this reaction; these factors can discriminate the differences in the reactivity and regioselectivity among the Brønsted acids used in this reaction. In the presence of Lewis acid Sn(OTf)2, a butatrienecyclopane can produce the corresponding ring‐opened products in moderate yields. 相似文献
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A palladium-catalyzed cycloisomerisation reaction of 1,6-enyne acetic esters have been developed. This cyclization reaction shows excellent regioselectivity and good functional group tolerance to obtain five-membered nitrogenated heterocyclic conjugated trienes in moderate to excellent yields. The resulting conjugated trienes could be facilely converted to highly substituted benzenes through Diels-Alder reactions. 相似文献