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81.
Rhodium(III)‐Catalyzed [3+2]/[5+2] Annulation of 4‐Aryl 1,2,3‐Triazoles with Internal Alkynes through Dual C(sp2)H Functionalization 下载免费PDF全文
Yuan Yang Ming‐Bo Zhou Xuan‐Hui Ouyang Rui Pi Dr. Ren‐Jie Song Prof. Dr. Jin‐Heng Li 《Angewandte Chemie (International ed. in English)》2015,54(22):6595-6599
A rhodium(III)‐catalyzed [3+2]/[5+2] annulation of 4‐aryl 1‐tosyl‐1,2,3‐triazoles with internal alkynes is presented. This transformation provides straightforward access to indeno[1,7‐cd]azepine architectures through a sequence involving the formation of a rhodium(III) azavinyl carbene, dual C(sp2)? H functionalization, and [3+2]/[5+2] annulation. 相似文献
82.
One‐Pot Cannizzaro Cascade Synthesis of ortho‐Fused Cycloocta‐2,5‐dien‐1‐ones from 2‐Bromo(hetero)aryl Aldehydes 下载免费PDF全文
Dr. Laurence Burroughs Lee Eccleshare John Ritchie Omkar Kulkarni Prof. Dr. Barry Lygo Prof. Dr. Simon Woodward Dr. William Lewis 《Angewandte Chemie (International ed. in English)》2015,54(36):10648-10651
An intramolecular Cannizzaro‐type hydride transfer to an in situ prepared allene enables the synthesis of ortho‐fused 4‐substituted cycloocta‐2,5‐dien‐1‐ones with unprecedented technical ease for an eight‐ring carboannulation. Various derivatives could be obtained from commercially available (hetero)aryl aldehydes, trimethylsilylacetylene, and simple propargyl chlorides in good yields. 相似文献
83.
Hydroxoiridium/Chiral Diene Complexes as Effective Catalysts for Asymmetric Annulation of α‐Oxo‐ and Iminocarboxamides with 1,3‐Dienes 下载免费PDF全文
Miyuki Hatano Dr. Takahiro Nishimura 《Angewandte Chemie (International ed. in English)》2015,54(37):10949-10952
The asymmetric [3+2] annulation of α‐oxo‐ and α‐iminocarboxamides with 1,3‐dienes catalyzed by hydroxoiridium/chiral diene complexes was realized, giving high yields of the corresponding γ‐lactams with high enantioselectivity. 相似文献
84.
Sulfur‐Annulated Hexa‐peri‐hexabenzocoronene Decorated with Phenylthio Groups at the Periphery 下载免费PDF全文
Dr. Yuan‐Zhi Tan Dr. Silvio Osella Yi Liu Bo Yang Prof. Dr. David Beljonne Prof. Dr. Xinliang Feng Prof. Dr. Klaus Müllen 《Angewandte Chemie (International ed. in English)》2015,54(10):2927-2931
The chemical nature of the edge periphery essentially determines the physical properties of graphene. As a molecular‐level model system, large polycyclic aromatic hydrocarbons, that is, so‐called nanographenes, can be chemically modified through either edge functionalization or doping with heteroatoms. Although the synthetic methods for edge substitution are well‐developed, incorporation with heteroatoms by the bay annulation of large PAHs remains an enormous challenge. In this study, we present a feasible peripheral sulfur annulation of hexa‐peri‐hexabenzocoronene (HBC) by thiolation of perchlorinated HBC. The tri‐sulfur‐annulated HBC and di‐sulfur‐annulated HBC decorated with phenylthio groups were obtained and characterized by X‐ray diffraction, revealing their distinct sulfur‐annulated peripheral structure. Associated with theoretical calculations, we propose that the regioselective sulfur annulation results from the minimization of strain in the aromatic backbone. We further demonstrate the structure‐correlated property modulation by sulfur annulation, manifested by a decrease in band gap and tunable redox activity. 相似文献
85.
Intermolecular Dynamic Kinetic Resolution Cooperatively Catalyzed by an N‐Heterocyclic Carbene and a Lewis Acid 下载免费PDF全文
Zijun Wu Fangyi Li Prof. Dr. Jian Wang 《Angewandte Chemie (International ed. in English)》2015,54(5):1629-1633
The ubiquitous structure of δ‐lactones makes the development of new methods for their enantioselective and stereoselective synthesis an important ongoing challenge. The intermolecular dynamic kinetic resolution (DKR) of β‐halo‐α‐ketoesters cooperatively catalyzed by an N‐heterocyclic carbene and a Lewis acid generates two contiguous stereocenters with remarkable diastereoselectivity through an oxidation/lactonization sequence. 相似文献
86.
Rhodium(II)‐Catalyzed Annulation of Azavinyl Carbenes Through Ring‐Expansion of 1,3,5‐Trioxane: Rapid Access to Nine‐Membered 1,3,5,7‐Trioxazonines 下载免费PDF全文
Dr. Jola Pospech Dr. Raffaella Ferraccioli Dr. Helfried Neumann Prof. Dr. Matthias Beller 《化学:亚洲杂志》2015,10(12):2624-2630
The rhodium(II)‐catalyzed denitrogenative coupling of N‐alkylsulfonyl 1,2,3‐triazoles with 1,3,5‐trioxane led to nine‐membered‐ringed trioxazonines in moderate‐to‐good yields. 1,3,5‐Trioxane, acting as an oxygen nucleophile, reacted with the α‐aza‐vinylcarbene intermediate, giving rise to ylide formation, which was probably the key step in the reaction. Triazoles that contained aryl substituents with various electronic and steric features on the C4 carbon atom were well‐tolerated. The synthesis of trioxazonine derivatives was achieved through a one‐pot, two‐step procedure from 1‐mesylazide and a terminal alkyne by combining CuI‐catalyzed 1,3‐dipolar cycloaddition and rhodium‐catalyzed transformations. 相似文献
87.
The unusual tricyclo[6.4.0.04.9]dodecane framework was constructed in eight linear steps in 13%overall yield.An innovative strategy accessing the framework from bicyclo[3.3.1]nonanes was employed.The key steps involve a Robinson annulation,a base induced decarboxylation and epimerization in a single step,and an intramolecular alkylation. 相似文献
88.
In this account, we provide a brief summary of recent developments in ruthenium‐catalyzed metathesis cascade reactions towards the total synthesis of natural products. We also highlight recent progress from our own laboratory regarding the synthesis of securinega alkaloids and humulanolides, which has resulted in the development of novel ruthenium‐catalyzed metathesis cascade reactions. Inspired and guided by the pioneering and elegant research conducted in this area, we developed a regio‐controlled relay dienyne metathesis cascade reaction and a cyclobutene‐promoted RCM/ROM/RCM cascade reaction for the synthesis of securinega alkaloids and humulanolides, respectively. 相似文献
89.
Pd-catalyzed cycloisomerization-allylation of 4-alkynones: synthesis of 5-homoallylfuran derivatives
Akio Saito 《Tetrahedron letters》2011,52(33):4299-4302
In the presence of Pd2(dba)3-tBu3P catalyst and Cs2CO3, cycloisomerization-allylation reactions of 4-alkynone derivatives with allyl carbonates in MeCN proceed in 5-exo mode to give highly-substituted furans having homoallyl groups at 5-position. 相似文献
90.
Convergent Synthesis of 2H-Chromenes - a Formal [3+3] Cycloaddition by a One-pot, Three-Step Cascade
In cases in which the palladium-catalyzed coupling of a bromoquinone with a vinyl stannane affords a vinyl quinone that enolizes, the resulting ortho-quinone methide undergoes an oxa-6π electrocyclization. Enolization is promoted by the presence of a polar additive. The net conversion is a formal [3+3] cycloaddition that gives 2H-chromenes. Because the first two steps of the cascade are catalyzed, the overall conversion is an example of multicatalysis. Yields for the optimized, one-pot protocol are dramatically improved over the conventional stepwise process. 相似文献