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221.
A General Catalytic Hydroamidation of 1,3‐Dienes: Atom‐Efficient Synthesis of N‐Allyl Heterocycles,Amides, and Sulfonamides 下载免费PDF全文
Dr. Debasis Banerjee Dr. Kathrin Junge Prof. Dr. Matthias Beller 《Angewandte Chemie (International ed. in English)》2014,53(6):1630-1635
Transition‐metal‐catalyzed hydroamination reactions are sustainable and atom‐economical C? N bond‐forming processes. Although remarkable progress has been made in the inter‐ and intramolecular amination of olefins and 1,3‐dienes, related intermolecular reactions of amides are still much less known. Control of the regioselectivity without analogous telomerization is the particular challenge in the catalytic hydroamidation of alkenes and 1,3‐dienes. Herein, we report a general protocol for the hydroamidation of electron‐deficient N‐heterocyclic amides and sulfonamides with 1,3‐dienes and vinyl pyridines in the presence of a catalyst derived from [{Pd(π‐cinnamyl)Cl}2] and ligand L7 or L10 . The reactions proceeded in good to excellent yield with high regioselectivity. The practical utility of our method is demonstrated by the hydroamidation of functionalized biologically active substrates. The high regioselectivity for linear amide products makes the procedure useful for the synthesis of a variety of allylic amides. 相似文献
222.
Dr. Debasis Banerjee Dr. Rajenahally V. Jagadeesh Dr. Kathrin Junge Dr. Marga‐Martina Pohl Dr. Jörg Radnik Prof. Dr. Angelika Brückner Prof. Dr. Matthias Beller 《Angewandte Chemie (International ed. in English)》2014,53(17):4359-4363
A general epoxidation of aromatic and aliphatic olefins has been developed under mild conditions using heterogeneous CoxOy–N/C (x=1,3; y=1,4) catalysts and tert‐butyl hydroperoxide as the terminal oxidant. Various stilbenes and aliphatic alkenes, including renewable olefins, and vitamin and cholesterol derivatives, were successfully transformed into the corresponding epoxides with high selectivity and often good yields. The cobalt oxide catalyst can be recycled up to five times without significant loss of activity or change in structure. Characterization of the catalyst by XRD, TEM, XPS, and EPR analysis revealed the formation of cobalt oxide nanoparticles with varying size (Co3O4 with some CoO) and very few large particles with a metallic Co core and an oxidic shell. During the pyrolysis process the nitrogen ligand forms graphene‐type layers, in which selected carbon atoms are substituted by nitrogen. 相似文献
223.
Regio‐ and Diastereoselective and Enantiospecific Metal‐Free C(sp3)H Arylation: Facile Access to Optically Active 5‐Aryl 2,5‐Disubstituted Pyrrolidines 下载免费PDF全文
Surajit Haldar Subhra Kanti Roy Bholanath Maity Prof. Dr. Debasis Koley Prof. Dr. Chandan K. Jana 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(43):15290-15298
Optically active 5‐aryl 2,5‐disubstituted pyrrolidines are the principal structural moiety of many bioactive compounds including natural products and catalysts for asymmetric synthesis. A highly regio‐ and diastereoselective and enantiospecific method for direct C?H arylation of aliphatic amine has been developed. Structurally diverse enantiopure arylated pyrrolidines were synthesized from commercially available starting materials, through a single‐step three‐component reaction under metal‐ and oxidant‐free conditions. Furthermore, the complex analogous structure of CCK antagonist RP 66803 and angiotensin‐converting enzyme inhibitors was easily constructed using the synthesized arylated pyrrolidine derivative. Detailed theoretical calculations (M06‐2X/TZVPP/SMD//M06‐2X/6‐31+G(d,p) level) were also carried to investigate the mechanism and high level of stereocontrol involved in this direct sp3 C?H arylation reaction. Preference for a given regio‐ and stereoselectivity in the arylated product can be explained through elucidation of the mechanism for dehydration, generating azomethine ylide, and for the final re‐aromatization step. The calculated energies reveals that the re‐aromatization step is essentially rate determining, accompanying an activation barrier of Δ≠${G{{{\rm S}\hfill \atop {\rm L}\hfill}}}$ =25.6 kcal mol?1. 相似文献
224.
Asymptotic properties of the least squares estimators of the parameters of the chirp signals 总被引:1,自引:0,他引:1
Chirp signals are quite common in different areas of science and engineering. In this paper we consider the asymptotic properties
of the least squares estimators of the parameters of the chirp signals. We obtain the consistency property of the least squares
estimators and also obtain the asymptotic distribution under the assumptions that the errors are independent and identically
distributed. We also consider the generalized chirp signals and obtain the asymptotic properties of the least squares estimators
of the unknown parameters. Finally we perform some simulations experiments to see how the asymptotic results behave for small
sample and the performances are quite satisfactory. 相似文献
225.
This paper applies nonlinear goal programming (NLGP) to obtain the economic order quantity (EOQ) in a multi-item inventory
problem. The model demonstrates how the appropriate priority structure can be selected to determine the optimum EOQ. Sensitivity
analysis on the weight structure in a priority structure of the goals has been performed to obtain different solutions in
the decision-making environment. The ideal solution is the identified among the solutions associated with different weight
structures. The minimum ofd
1 distances from different solutions to the ideal solution identifies the most acceptable solution. The associated weight structure
will be the appropriate weight structure according to the decision-making situation. The effectiveness of the NLGP model is
demonstrated via an example. 相似文献
226.
227.
Kalipada Koner Suvendu Karak Yutaro Ogaeri Yusuke Nishiyama Rahul Banerjee 《Angewandte Chemie (International ed. in English)》2023,62(20):e202300652
Covalent organic nanotubes (CONTs) are porous one-dimensional frameworks connected through imine bonds via Schiff base condensation between aldehydes and amines. The presence of two amine groups at the ortho position in the structurally demanding tetraaminotriptycene (TAT) building block leads to multiple reaction pathways between the ditopic aldehyde and the tetratopic amine. We have synthesized five different monomers of CONT-1 by the Schiff base condensation reaction between TAT and o-anisaldehyde. The conversion of imine to imidazole bonding in a monomer is probed using NMR, mass spectrometry, and X-ray diffraction techniques. Solid-state NMR provide insights into the CONTs’ structural connectivity. A theoretical investigation suggests that the π-π stacking could be the driving force for rapid imine to imidazole conversion within the CONT-1. Microscopic imaging sheds further light on the self-assembly process of the CONTs, indicating both head-to-head and side-by-side assembly. 相似文献
228.
Samir Manna Swagata Paul Wang-Yeuk Kong Debasis Aich Rupam Sahoo Prof. Dean J. Tantillo Prof. Santanu Panda 《Angewandte Chemie (International ed. in English)》2023,62(38):e202309136
Stereoselective Zweifel olefination using boronate complexes carrying two different reactive π-systems was achieved to synthesize vinyl heteroarenes and conjugated 1,3-dienes in good yield and up to 100 % stereoselectivity, which remains unexplored until now. Most importantly, we report the unprecedented formation of E vs. Z-vinyl heteroarenes for different heteroarenes under identical conditions. Density functional theory (DFT) investigations unveil the mechanistic dichotomy between olefin and heteroarene activation followed by 1,2-migration, leading to E or Z-vinyl heteroarenes respectively. We also report a previously unknown reversal of stereoselectivity by using 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as an electrophile. The Zweifel olefination using a boronate complex that carries two different olefins was previously unexplored due to significant challenges associated with the site-selective activation of olefins. We have solved this problem and reported the site-selective activation of olefins for the stereoselective synthesis of 1,3-dienes. 相似文献
229.
Sen D Spalla O Taché O Haltebourg P Thill A 《Langmuir : the ACS journal of surfaces and colloids》2007,23(8):4296-4302
Nanoparticles confined in droplets of less than a picoliter are forced to organize in submicronic dry grains through solvent evaporation. The evolution of structures of the grains and the constituent nanoparticles during the slow drying process are investigated in situ with small-angle X-ray scattering (SAXS) for the first time. The scattering results have been explained on the basis of the equilibrium thermodynamics of the droplets in the drying tube. We demonstrate that this technique is really efficient in describing the internal arrangement of the nanoparticles inside the drying droplets. Distinction between an almost homogeneous repartition of the nanoparticles in droplets and formation of core shell like particles even in strongly polydispersed droplets can be made using SAXS. 相似文献
230.
[structure: see text] The potential antitumor agent (-)-dictyostatin has been synthesized utilizing Brown crotylboration to achieve eight of the eleven chiral centers. The yield for the 26-step longest sequence is approximately 4%. The C9-C10 coupling is achieved via a stereoselective vinylzincate addition. 相似文献