共查询到20条相似文献,搜索用时 15 毫秒
1.
Mechanistic Study on Rh‐Catalyzed Stereoselective CC/CH Activation of tert‐Cyclobutanols 下载免费PDF全文
Dr. Haizhu Yu Dr. Chen Wang Yimeng Yang Prof. Zhi‐Min Dang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(13):3839-3848
A mechanistic study was performed on the Rh‐catalyzed stereoselective C?C/C?H activation of tert‐cyclobutanols. The present study corroborated the previous proposal that the reaction occurs by metalation, β‐C elimination, 1,4‐Rh transfer, C?O insertion, and a final catalyst‐regeneration step. The rate‐determining step was found to be the 1,4‐Rh transfer step, whereas the stereoselectivity‐determining step did not correspond to any of the aforementioned steps. It was found that both the thermodynamic stability of the product of the β‐C elimination and the kinetic feasibility of the 1,4‐Rh transfer and C?O insertion steps made important contributions. In other words, three steps (i.e., β‐C elimination, 1,4‐Rh transfer, and C?O insertion) were found to be important in determining the configurations of the two quaternary stereocenters. 相似文献
2.
Palladium‐Catalyzed Construction of Heteroatom‐Containing π‐Conjugated Systems by Intramolecular Oxidative CH/CH Coupling Reaction 下载免费PDF全文
Kenta Saito Dr. Prasanna Kumara Chikkade Prof. Dr. Motomu Kanai Prof. Dr. Yoichiro Kuninobu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(23):8365-8368
Synthesis of heteroatom‐containing ladder‐type π‐conjugated molecules was successfully achieved via a palladium‐catalyzed intramolecular oxidative C?H/C?H cross‐coupling reaction. This reaction provides a variety of π‐conjugated molecules bearing heteroatoms, such as nitrogen, oxygen, phosphorus, and sulfur atoms, and a carbonyl group. The π‐conjugated molecules were synthesized efficiently, even in gram scale, and larger π‐conjugated molecules were also obtained by a double C?H/C?H cross‐coupling reaction and successive oxidative cycloaromatization. 相似文献
3.
Rhodium(III)‐Catalyzed Three‐Component Reaction of Imines,Alkynes, and Aldehydes through CH Activation 下载免费PDF全文
Ji‐Rong Huang Qiang Song Yu‐Qin Zhu Liu Qin Prof. Dr. Zhi‐Yong Qian Prof. Dr. Lin Dong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):16882-16886
An efficient rhodium(III)‐catalyzed tandem three‐component reaction of imines, alkynes and aldehydes through C?H activation has been developed. High stereo‐ and regioselectivity, as well as good yields were obtained in most cases. The simple and atom‐economical approach offers a broad scope of substrates, providing polycyclic skeletons with potential biological properties. 相似文献
4.
Palladium‐Catalyzed Annulation of Diarylamines with Olefins through CH Activation: Direct Access to N‐Arylindoles 下载免费PDF全文
Dr. Upendra Sharma Dr. Rajesh Kancherla Togati Naveen Soumitra Agasti Prof. Debabrata Maiti 《Angewandte Chemie (International ed. in English)》2014,53(44):11895-11899
A palladium‐catalyzed dehydrogenative coupling between diarylamines and olefins has been discovered for the synthesis of substituted indoles. This intermolecular annulation approach incorporates readily available olefins for the first time and obviates the need of any additional directing group. An ortho palladation, olefin coordination, and β‐migratory insertion sequence has been proposed for the generation of olefinated intermediate, which is found to produce the expected indole moiety. 相似文献
5.
Palladium‐Catalyzed Synthesis of Phenanthridine/Benzoxazine‐Fused Quinazolinones by Intramolecular CH Bond Activation 下载免费PDF全文
Puneet K. Gupta Nisha Yadav Subodh Jaiswal Mohd. Asad Dr. Ruchir Kant Dr. Kanchan Hajela 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(38):13210-13215
A highly efficient synthesis of phenanthridine/benzoxazine‐fused quinazolinones by ligand‐free palladium‐catalyzed intramolecular C?H bond activation under mild conditions has been developed. The C?C coupling provides the corresponding N‐fused polycyclic heterocycles in good to excellent yields and with wide functional group tolerance. 相似文献
6.
Dr. Rishikesh Narayan Dr. Kiran Matcha Dr. Andrey P. Antonchick 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):14678-14693
The formation of C?C bonds embodies the core of organic chemistry because of its fundamental application in generation of molecular diversity and complexity. C?C bond‐forming reactions are well‐known challenges. To achieve this goal through direct functionalization of C?H bonds in both of the coupling partners represents the state‐of‐the‐art in organic synthesis. Oxidative C?C bond formation obviates the need for prefunctionalization of both substrates. This Minireview is dedicated to the field of C?C bond‐forming reactions through direct C?H bond functionalization under completely metal‐free oxidative conditions. Selected important developments in this area have been summarized with representative examples and discussions on their reaction mechanisms. 相似文献
7.
Amidines for Versatile Ruthenium(II)‐Catalyzed Oxidative CH Activations with Internal Alkynes and Acrylates 下载免费PDF全文
Jie Li Dr. Michael John Prof. Dr. Lutz Ackermann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(18):5403-5408
Cationic ruthenium complexes derived from KPF6 or AgOAc enabled efficient oxidative C?H functionalizations on aryl and heteroaryl amidines. Thus, oxidative annulations of diversely decorated internal alkynes provided expedient access to 1‐aminoisoquinolines, while catalyzed C?H activations with substituted acrylates gave rise to structurally novel 1‐iminoisoindolines. The powerful ruthenium(II) catalysts displayed a remarkably high site‐, regio‐ and, chemoselectivity. Therefore, the catalytic system proved tolerant of a variety of important electrophilic functional groups. Detailed mechanistic studies provided strong support for the cationic ruthenium(II) catalysts to operate by a facile, reversible C?H activation. 相似文献
8.
9.
Rhodium(III)‐Catalyzed CC and CO Coupling of Quinoline N‐Oxides with Alkynes: Combination of CH Activation with O‐Atom Transfer 下载免费PDF全文
Xueyun Zhang Zisong Qi Prof. Xingwei Li 《Angewandte Chemie (International ed. in English)》2014,53(40):10794-10798
[Cp*RhIII]‐catalyzed C? H activation of arenes assisted by an oxidizing N? O or N? N directing group has allowed the construction of a number of hetercycles. In contrast, a polar N? O bond is well‐known to undergo O‐atom transfer (OAT) to alkynes. Despite the liability of N? O bonds in both C? H activation and OAT, these two important areas evolved separately. In this report, [Cp*RhIII] catalysts integrate both areas in an efficient redox‐neutral coupling of quinoline N‐oxides with alkynes to afford α‐(8‐quinolyl)acetophenones. In this process the N? O bond acts as both a directing group for C? H activation and as an O‐atom donor. 相似文献
10.
M. Sc. Keshav Raghuvanshi Karsten Rauch Prof. Lutz Ackermann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1790-1794
Intermolecular C?H acyloxylations of phenols with removable directing groups were accomplished with a versatile ruthenium catalyst. Specifically, a cationic ruthenium(II) complex, formed in situ, enabled the chemoselective C?H oxygenations of a broad range of substrates. The catalyst proved tolerant of synthetically valuable functional groups, and the substrate scope included both (hetero)aromatic and, the more challenging, aliphatic carboxylic acids. The proposed reaction mechanism involves a reversible C?H ruthenation and an oxidatively induced C?O‐bond‐forming reductive elimination. 相似文献
11.
Manganese‐Catalyzed Synthesis of cis‐β‐Amino Acid Esters through Organometallic CH Activation of Ketimines 下载免费PDF全文
M. Sc. Weiping Liu M. Sc. Daniel Zell Dr. Michael John Prof. Dr. Lutz Ackermann 《Angewandte Chemie (International ed. in English)》2015,54(13):4092-4096
Manganese‐catalyzed C? H functionalization reactions of ketimines set the stage for the expedient synthesis of cis‐β‐amino acid esters through site‐ and regioselective alkene annulations. The organometallic C? H activation occurred efficiently with high functional group tolerance, delivering densely functionalized β‐amino acid derivatives with ample scope. 相似文献
12.
Ruthenium(II)‐Catalyzed Synthesis of Isochromenes by CH Activation with Weakly Coordinating Aliphatic Hydroxyl Groups 下载免费PDF全文
Sachiyo Nakanowatari Prof. Dr. Lutz Ackermann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(18):5409-5413
Cationic ruthenium(II) complexes have been employed for the highly effective oxidative annulation of alkynes with benzyl alcohols to deliver diversely decorated isochromenes. The hydroxyl‐directed C?H/O?H functionalization process proceeded efficiently under an atmosphere of air. Detailed mechanistic studies were indicative of a kinetically relevant C?H metalation. 相似文献
13.
Palladium‐Catalyzed/Norbornene‐Mediated CH Activation/ N‐Tosylhydrazone Insertion Reaction: A Route to Highly Functionalized Vinylarenes 下载免费PDF全文
Dr. Ping‐Xin Zhou Lan Zheng Jun‐Wei Ma Yu‐Ying Ye Xue‐Yuan Liu Prof. Dr. Peng‐Fei Xu Prof. Dr. Yong‐Min Liang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6745-6751
A straightforward method for the synthesis of highly functionalized vinylarenes through palladium‐catalyzed, norbornene‐mediated C?H activation/carbene migratory insertion is described. Extension to a one‐pot procedure is also developed. Furthermore, this method can also be used to generate polysubstituted bicyclic molecules. The reaction proceeds under mild conditions to give the products in satisfactory yields using readily available starting materials. This is a Catellani–Lautens reaction that incorporates different types of coupling partners. Additionally, this reaction is the first to demonstrate the possibility of combining Pd‐catalyzed insertion of diazo compounds and Pd‐catalyzed C?H activation. 相似文献
14.
Highly Enantioselective Rhodium(I)‐Catalyzed Activation of Enantiotopic Cyclobutanone CC Bonds 下载免费PDF全文
Laetitia Souillart Dr. Evelyne Parker Prof. Dr. Nicolai Cramer 《Angewandte Chemie (International ed. in English)》2014,53(11):3001-3005
The selective functionalization of carbon–carbon σ bonds is a synthetic strategy that offers uncommon retrosynthetic disconnections. Despite progress in C? C activation and its great importance, the development of asymmetric reactions lags behind. Rhodium(I)‐catalyzed selective oxidative additions into enantiotopic C? C bonds in cyclobutanones are reported. Even operating at a reaction temperature of 130 °C, the process is characterized by outstanding enantioselectivity with the e.r. generally greater than 99.5:0.5. The intermediate rhodacycle is shown to react with a wide variety of tethered olefins to deliver complex bicyclic ketones in high yields. 相似文献
15.
Chao Feng Prof. Dr. Teck‐Peng Loh 《Angewandte Chemie (International ed. in English)》2014,53(10):2722-2726
The rhodium(III)‐catalyzed ortho C? H alkynylation of non‐electronically activated arenes is disclosed. This process features a straightforward and highly effective protocol for the synthesis of functionalized alkynes and represents the first example of merging a hypervalent iodine reagent with rhodium(III) catalysis. Notably, this reaction proceeds at room temperature, tolerates a variety of functional groups, and more importantly, exhibits high selectivity for monoalkynylation. 相似文献
16.
Highly Enantioselective Rhodium(I)‐Catalyzed Carbonyl Carboacylations Initiated by CC Bond Activation 下载免费PDF全文
Laetitia Souillart Prof. Dr. Nicolai Cramer 《Angewandte Chemie (International ed. in English)》2014,53(36):9640-9644
The lactone motif is ubiquitous in natural products and pharmaceuticals. The Tishchenko disproportionation of two aldehydes, a carbonyl hydroacylation, is an efficient and atom‐economic access to lactones. However, these reaction types are limited to the transfer of a hydride to the accepting carbonyl group. The transfer of alkyl groups enabling the formation of C? C bonds during the ester formation would be of significant interest. Reported herein is such asymmetric carbonyl carboacylation of aldehydes and ketones, thus affording complex bicyclic lactones in excellent enantioselectivities. The rhodium(I)‐catalyzed transformation is induced by an enantiotopic C? C bond activation of a cyclobutanone and the formed rhodacyclic intermediate reacts with aldehyde or ketone groups to give highly functionalized lactones. 相似文献
17.
Palladium(0)‐Catalyzed Heck Reaction/CH Activation/Amination Sequence with Diaziridinone: A Facile Approach to Indolines 下载免费PDF全文
Dr. Huaiji Zheng Dr. Yingguang Zhu Prof. Dr. Yian Shi 《Angewandte Chemie (International ed. in English)》2014,53(42):11280-11284
Indolines are important moieties present in various biologically significant molecules and have attracted considerable attention in synthetic chemistry. This paper describes a Heck reaction/C? H activation/amination sequence for forming indolines using di‐tert‐butyldiaziridinone. The reaction process likely proceeds via a pallada(II)cycle, which is converted into an indoline by oxidative addition to the diaziridinone and two subsequent C? N bond formations. 相似文献
18.
One‐Pot Synthesis of Highly Substituted Polyheteroaromatic Compounds by Rhodium(III)‐Catalyzed Multiple CH Activation and Annulation 下载免费PDF全文
Jayachandran Jayakumar Dr. Kanniyappan Parthasarathy Yi‐Hsiang Chen Tai‐Hua Lee Prof. Dr. Shih‐Ching Chuang Prof. Dr. Chien‐Hong Cheng 《Angewandte Chemie (International ed. in English)》2014,53(37):9889-9892
A new method for the synthesis of highly substituted naphthyridine‐based polyheteroaromatic compounds in high yields proceeds through rhodium(III)‐catalyzed multiple C? H bond cleavage and C? C and C? N bond formation in a one‐pot process. Such highly substituted polyheteroaromatic compounds have attracted much attention because of their unique π‐conjugation, which make them suitable materials for organic semiconductors and luminescent materials. Furthermore, a possible mechanism, which involves multiple chelation‐assisted ortho C? H activation, alkyne insertion, and reductive elimination, is proposed for this transformation. 相似文献
19.
Manganese‐Catalyzed Dehydrogenative [4+2] Annulation of NH Imines and Alkynes by CH/NH Activation 下载免费PDF全文
Ruoyu He Prof. Dr. Zhi‐Tang Huang Prof. Dr. Qi‐Yu Zheng Prof. Dr. Congyang Wang 《Angewandte Chemie (International ed. in English)》2014,53(19):4950-4953
Described herein is a manganese‐catalyzed dehydrogenative [4+2] annulation of N? H imines and alkynes, a reaction providing highly atom‐economical access to diverse isoquinolines. This transformation represents the first example of manganese‐catalyzed C? H activation of imines; the stoichiometric variant of the cyclomanganation was reported in 1971. The redox neutral reaction produces H2 as the major byproduct and eliminates the need for any oxidants, external ligands, or additives, thus standing out from known isoquinoline synthesis by transition‐metal‐catalyzed C? H activation. Mechanistic studies revealed the five‐membered manganacycle and manganese hydride species as key reaction intermediates in the catalytic cycle. 相似文献
20.
Copper‐Catalyzed Dehydrogenative Cross‐Coupling Reaction between Allylic CH Bonds and α‐CH Bonds of Ketones or Aldehydes 下载免费PDF全文
Xing‐Fen Huang Muhammad Salman Prof. Zhi‐Zhen Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6618-6621
A dehydrogenative cross‐coupling reaction between allylic C?H bonds and the α‐C?H bond of ketones or aldehydes was developed using Cu(OTf)2 as a catalyst and DDQ as an oxidant. This synthetic approach to γ,δ‐unsaturated ketones and aldehydes has the advantages of broad scope for both ketones and aldehydes as reactants, mild reaction conditions, good yields and atom economy. A plausible mechanism using Cu(OTf)2 as a Lewis acid catalyst was also proposed (DDQ=2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone; Tf=trifluoromethanesulfonate). 相似文献