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11.
Florian Blaser Pierre-Franois Deschenaux Thomas Kallimopoulos Andr Jacot-Guillarmod 《Helvetica chimica acta》1991,74(4):787-790
Synthesis of (?)-(6R)- and (+)-(6S)-Tetrahydro-6-[(Z)-pent-2-enyl]-2H-Pyran-2-one, lactones from Jasminum grandiflorum L. and from Polianthes tuberosa L. (?)-(2S)-Ethyl 2-hydroxyhexanedioate ((2S)- 2 ) was obtained by kinetic resolution of racemic ethyl 2-hydroxy-hexanedioate with baker's yeast. The key intermediates (+)-(5R)- and (?)-(5S)-ethyl 5,6-epoxyhexanoate ((5R)- and (5S)- 6 , resp.) are proved to be useful synthons for the total synthesis of chiral 6-alkyl-δ-lactones, as exemplified by the preparation of both enantiomers of jasmine lactone ((6R)- and (6S)- 10 , resp.). 相似文献
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Hans-Ulrich Gonzenbach Inga-Mai Tegmo-Larsson Jean-Pierre Grosclaude Kurt Schaffner 《Helvetica chimica acta》1977,60(3):1091-1123
2-Cyclopentenyl and 3-phenyl-2-cyclopentenyl methyl ketones (15–18, 30, 31) undergo a 1,3-acetyl shift on direct irradiation, and the oxa-di-π-methane rearrangement to photochemically non-interconverting endo and exo bicyclo-[2.1.0]pentyl methyl ketones on triplet sensitization. Exceptions include the 2-methyl-3-phenyl-2-cyclopentenyl methyl ketone 32 and the 1-phenyl-2-cyclo-pentenyl methyl ketone 44 which are unreactive on direct irradiation and on triplet sensitization, respectively, and the 2-phenyl-2-cyclopentenyl methyl ketones 42 and 43 which do not react under either condition. The reactive triplet of the 3-phenyl-2-cyclopentenyl methyl ketone 30 has been identified as the localized styrene π,π*-state of ET=59 kcal/mol by comparison of its phosphorescence at 77K in rigid glasses with that of 1-phenyl-cyclopentene, and by the independence of the quantum yield on sensitizer energy in the range of 61–74 kcal/mol. 相似文献
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The chemistry of [Re(CO)(NO)L2] fragments (L ? phosphorus donor) was explored. Starting from [Re(CO)5Cl] the synthesis of [Re2Cl2(μ-Cl)2(CO)4(NO)2] ( 1 ) was accomplished via the preparation of [Et4N]2[Re2Cl2(μ-Cl)2(CO)6] and nitrosylation of this compound with [NO][BF4]. Complex 1 was converted to [RecL2(CO)(NO)L2] complexes 2 ( a L = (MeO)3P; b L = (EtO)3P; c L = (i-PrO)3P; d L ? Me3P; e L ? Et3P; f L ? Cy3P) by heating with L in MeCN. In the case of the reaction of L = (MeO)3P, a trisubstitued compound mer-{ReCl2(NO)[P(OMe)3]3} 3 was also obtained. Replacement of the Cl ligands in 2a–e with Me groups was achieved by reacting them with MeLi in Et2O yielding cis, trans-[Re(CO)(NO)Me2L2]complexes 4a–e . Reaction of 2a–e with Li[BHEt3] led to substitution of one Cl by an H ligand with formation of [ReCl(CO)H(NO)L2] compounds 5a–;e , displaying trans-H,NO geometries. The hydride-transfer agent Na[AlH2(OCH2CH2OCH3)2] transformed 2 into the cis-dihydride systems [Re(CO)H2(NO)L2] 6a–f . Reductive carbonylation of 2a–d in the presence of Na/Hg and CO gave pentacoordinate [Re(CO)2(NO)L2] complexes 7b–d , and under comparable conditions the Cl substituents of 2b–f were replaced by tolane using Mg or t-BuLi giving trigonal bipyramidal [Re(CO)(NO)L2(PhC?CPh)] compounds 8b–f . Complexes 5c , 6a , and 8d were characterized by X-ray crystal-structure analysis. 相似文献
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Dr. Christine Beemelmanns Dr. Dominik Nitsch Dr. Christoph Bentz Prof. Dr. Hans-Ulrich Reissig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8780-8789
A series of γ-indolylketones with fluorine, cyano or alkoxy substituents at the benzene moiety was prepared and subjected to samarium diiodide-promoted cyclization reactions. The desired dearomatizing ketyl cascade reaction forming two new rings proceeded in all cases with high diastereoselectivity, but with differing product distribution. In most cases, the desired annulated tetracyclic compounds were obtained in moderate to good yields, but as second product tetracyclic spirolactones were isolated in up to 29 % yield. The reaction rate was influenced by the substituents at the benzene moiety of the substrate as expected, with electron-accepting groups accelerating and electron-donating groups decelerating the cyclization process. In case of a difluoro-substituted γ-indolylketone a partial defluorination was observed. The intermediate samarium enolate of the tetracyclic products could be trapped by adding reactive alkylating agents as electrophiles delivering products with quarternary carbons. In the case of a dimethoxy-substituted tetracyclic cyclization product a subsequent reductive amination stereoselectively provided a pentacyclic compound that was subsequently N-protected and subjected to a regioselective elimination. The obtained functionalized pentacyclic product should be convertible into the alkaloid brucine by four well-established steps. Overall, the presented report shows that functionalized tetracyclic compounds with different substituents are rapidly available with the samarium diiodide cascade cyclization as crucial step. Hence, analogues of the landmark alkaloid strychnine, for example, with specific fluorine substitutions, should be easily accessible. 相似文献
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Clemente-Juan JM Coronado E Gaita-Ariño A Giménez-Saiz C Chaboussant G Güdel HU Burriel R Mutka H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(24):5701-5708
The ground-state properties of a Co3II moiety encapsulated in a polyoxometalate anion were investigated by combining measurements of specific heat, magnetic susceptibility, and low-temperature magnetization with a detailed inelastic neutron scattering (INS) study on a fully deuterated polycrystalline sample of Na12[Co3W(D2O)2(ZnW9O34)2].40D2O (Co3). The ferromagnetic Co3O14 cluster core consists of three octahedrally oxo-coordinated CoII ions. According to the single-ion anisotropy and spin-orbit coupling of the octahedral CoII ions, the appropriate exchange Hamiltonian to describe the ground-state properties of the Co3 spin cluster is anisotropic and is expressed as H = -2 sigma a = x,y,z (Ja12 S1a S2a + Ja23 S2a S3a), where Ja are the components of the exchange interactions between the CoII ions. To reproduce the INS data, different orientations of the two anisotropic J tensors must be considered, and the following conditions had to be introduced: Jx12 = Jy23, Jy12 = Jx23, Jz12 = Jz23. This result was correlated with the molecular symmetry of the complex. The following set of parameters was obtained: Jx12 = Jy23 = 1.37, Jy12 = Jx23 = 0.218, and Jz12 = Jz23 = 1.24 meV. This set also reproduces in a satisfactory manner the specific heat, susceptibility, and magnetization properties of Co3. 相似文献
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