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1.
The cross-metathesis reaction of S-ethyl thioacrylate with a variety of olefins is effectively catalyzed by using a ruthenium benzylidene olefin metathesis catalyst. This reaction provides a convenient and versatile route to substituted alpha,beta-unsaturated thioesters, key building blocks in organic synthesis. 相似文献
2.
Among the many types of transition-metal-catalyzed C-C bond-forming reactions, olefin metathesis has come to the fore in recent years owing to the wide range of transformations that are possible with commercially available and easily handled catalysts. Consequently, olefin metathesis is now widely considered as one of the most powerful synthetic tools in organic chemistry. Until recently the intermolecular variant of this reaction, cross-metathesis, had been neglected despite its potential. With the evolution of new catalysts, the selectivity, efficiency, and functional-group compatibility of this reaction have improved to a level that was unimaginable just a few years ago. These advances, together with a better understanding of the mechanism and catalyst-substrate interactions, have brought us to a stage where more and more researchers are employing cross-metathesis reactions in multistep procedures and in the synthesis of natural products. The recent inclusion of alkynes and hindered bicyclic olefins as viable substrates for bimolecular metathesis coupling, the discovery of enantioselective cross-metathesis and cross-metathesis in water, and the successful marriage of metathesis and solid-phase organic synthesis has further widened the scope of this versatile reaction. 相似文献
3.
Chatterjee AK Choi TL Sanders DP Grubbs RH 《Journal of the American Chemical Society》2003,125(37):11360-11370
In recent years, olefin cross metathesis (CM) has emerged as a powerful and convenient synthetic technique in organic chemistry; however, as a general synthetic method, CM has been limited by the lack of predictability in product selectivity and stereoselectivity. Investigations into olefin cross metathesis with several classes of olefins, including substituted and functionalized styrenes, secondary allylic alcohols, tertiary allylic alcohols, and olefins with alpha-quaternary centers, have led to a general model useful for the prediction of product selectivity and stereoselectivity in cross metathesis. As a general ranking of olefin reactivity in CM, olefins can be categorized by their relative abilities to undergo homodimerization via cross metathesis and the susceptibility of their homodimers toward secondary metathesis reactions. When an olefin of high reactivity is reacted with an olefin of lower reactivity (sterically bulky, electron-deficient, etc.), selective cross metathesis can be achieved using feedstock stoichiometries as low as 1:1. By employing a metathesis catalyst with the appropriate activity, selective cross metathesis reactions can be achieved with a wide variety of electron-rich, electron-deficient, and sterically bulky olefins. Application of this model has allowed for the prediction and development of selective cross metathesis reactions, culminating in unprecedented three-component intermolecular cross metathesis reactions. 相似文献
4.
Gold‐Catalyzed Asymmetric Allylic Substitution of Free Alcohols: An Enantioselective Approach to Chiral Chromans with Quaternary Stereocenters for the Synthesis of Vitamin E and Analogues
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Dr. Uxue Uria Dr. Carlos Vila Dr. Ming‐Yuan Lin Prof. Dr. Magnus Rueping 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(43):13913-13917
The enantioselective synthesis of α‐ and γ‐tocopherol (the most biologically active members of vitamin E family) and analogues has been accomplished employing a new enantioselective gold catalyzed intramolecular allylic alkylation reaction followed by an olefin cross‐metathesis as key steps. The methodology proved to be applicable to different olefins highlighting its potential for the synthesis of diverse libraries. 相似文献
5.
《Journal of organometallic chemistry》2007,692(1-3):554-561
Lewis acid-modified mesoporous alumina was found to be an efficient carrier as well as an activator for methyltrioxorhenium (MeReO3) in olefin metathesis reactions. Especially, MeReO3 doped on zinc chloride-modified mesoporous alumina catalyzed the metathesis of olefins with functional groups such as acetoxy, alkoxycarbonyl, acyl, chlorine, and bromine groups under mild conditions. The novel heterogeneous catalytic system promoted the metathesis of not only such functionalized olefins but also simple olefins without double bond migration that was often encountered on strong solid acids. We here present a new methodology for activation of a metal complex with Lewis acidic mesoporous materials in the metathesis reactions. This novel heterogeneous catalyst would be advantageous over conventional one from the viewpoint of environmental and economical organic synthesis. 相似文献
6.
Zhi‐Chao Cao Pei‐Lin Xu Qin‐Yu Luo Xiao‐Lei Li Da‐Gang Yu Huayi Fang Zhang‐Jie Shi 《中国化学》2019,37(8):781-785
A general and efficient protocol to synthesize substituted olefins from carbonyl compounds via nickel catalyzed C—O activation of enolates was developed. Besides ketones, aldehydes were also suitable substrates for the presented catalytic system to produce di‐ or tri‐ substituted olefins. It is worth noting that this approach exhibited good tolerance to highly reactive tertiary alcohols, which could not survive in other reported routes for converting carbonyl compounds to olefins. This method also showed good regio‐ and stereo‐selectivity for olefin products. Preliminary mechanistic studies indicated that the reaction was accomplished through nickel catalyzed C—O activation of enolates, thus offering helpful contribution to current enol chemistry. 相似文献
7.
Dr. Dmitry S. Belov Gabriela Tejeda Dr. Charlene Tsay Dr. Konstantin V. Bukhryakov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(14):4578-4582
Vanadium-based catalysts have shown activity and selectivity in ring-opening metathesis polymerization of strained cyclic olefins comparable to those of Ru, Mo, and W catalysts. However, the application of V alkylidenes in routine organic synthesis is limited. Here, we present the first example of ring-closing olefin metathesis catalyzed by well-defined V chloride alkylidene phosphine complexes. The developed catalysts exhibit tolerance to various functional groups, such as an ether, an ester, a tertiary amide, a tertiary amine, and a sulfonamide. The size and electron-donating properties of the imido group and the phosphine play a crucial role in the stability of active intermediates. Reactions with ethylene and olefins suggest that both β-hydride elimination of the metallacyclobutene and bimolecular decomposition are responsible for catalyst degradation. 相似文献
8.
The practical and convergent total synthesis of (+)-brefeldin A has been achieved by an olefin disconnection strategy. Key features of the total synthesis include the efficient formation of C2 and C10 olefins, employing an olefin cross metathesis (CM) reaction and an intramolecular HWE olefination, respectively. 相似文献
9.
Copper‐Catalyzed Trifluoromethylation of Internal Olefinic CH Bonds: Efficient Routes to Trifluoromethylated Tetrasubstituted Olefins and N‐Heterocycles
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Zhifeng Mao Fei Huang Dr. Haifeng Yu Prof. Dr. Jiping Chen Prof. Dr. Zhengkun Yu Prof. Dr. Zhaoqing Xu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(12):3439-3445
The functionalization of internal olefins has been a challenging task in organic synthesis. Efficient CuII‐catalyzed trifluoromethylation of internal olefins, that is, α‐oxoketene dithioacetals, has been achieved by using Cu(OH)2 as a catalyst and TMSCF3 as a trifluoromethylating reagent. The push–pull effect from the polarized olefin substrates facilitates the internal olefinic C?H trifluoromethylation. Cyclic and acyclic dithioalkyl α‐oxoketene acetals were used as the substrates and various substituents were tolerated. The internal olefinic C?H bond cleavage was not involved in the rate‐determining step, and a mechanism that involves radicals is proposed based on a TEMPO‐quenching experiment of the trifluoromethylation reaction. Further derivatization of the resultant CF3 olefins led to multifunctionalized tetrasubstituted CF3 olefins and trifluoromethylated N‐heterocycles. 相似文献
10.
Chenxi Wen Ting Li Prof. Dr. Zheng Huang Prof. Dr. Qi-Kai Kang 《Chemical record (New York, N.Y.)》2023,23(11):e202300146
Preparing valuable olefins from cheap and abundant alkane resources has long been a challenging task in organic synthesis, which mainly suffers from harsh reaction conditions and narrow scopes. Homogeneous transition metals catalyzed dehydrogenation of alkanes has attracted much attention for its excellent catalytic activities under relatively milder conditions. Among them, base metal catalyzed oxidative alkane dehydrogenation has emerged as a viable strategy for olefin synthesis for its usage of cheap catalysts, compatibility with various functional groups, and low reaction temperature. In this review, we discuss recent development of base metal catalyzed alkane dehydrogenation under oxidative conditions and their application in constructing complex molecules. 相似文献
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12.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(1):244-250
Vinyl‐substituted germanes react stereo‐ and regioselectively with olefins in the presence of complexes containing Ru? H and Ru? Ge bonds with the formation of functionalized vinylgermanes that cannot be synthesized by olefin cross‐metathesis procedures. The reaction opens a new catalytic route for preparation of a class of organogermanes that are potent organometallic reagents for organic synthesis because they show very low toxicity and could replace organotin compounds. The mechanism of this new catalytic route was proven to involve an interesting insertion of the vinylgermane into the Ru? H bond and β‐Ge transfer to the metal with elimination of ethylene and generation of an Ru? Ge bond, followed by insertion of the alkene into the Ru? Ge bond and β‐H transfer to the metal to eliminate the substituted vinylgermane. 相似文献
13.
Grzegorz K. Zieliński Prof. Dr. Karol Grela 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9440-9454
Since olefin metathesis transformation has become a favored synthetic tool in organic synthesis, more and more distinct non‐metathetical reactions of alkylidene ruthenium complexes have been developed. Depending on the conditions applied, the same olefin metathesis catalysts can efficiently promote isomerization reactions, hydrogenation of C=C double bonds, oxidation reactions, and many others. Importantly, these transformations can be carried out in tandem with olefin metathesis reactions. Through addition of one portion of a catalyst, a tandem process provides structurally advanced products from relatively simple substrates without the need for isolation of the intermediates. These aspects not only make tandem catalysis very attractive from a practical point of view, but also open new avenues in (retro)synthetic planning. However, in the literature, the term “tandem process” is sometimes used improperly to describe other types of multi‐reaction sequences. In this Concept, a number of examples of tandem catalysis involving olefin metathesis are discussed with an emphasis on their synthetic value. 相似文献
14.
With a view to understanding the role of the catalyst in olefin metathesis various attempts were made to synthesize possible intermediates of the reaction. No compound was formed which could account satisfactorily for a metathesis reaction under conditions favourable for the formation of tungstacyclopentane. Attempted synthesis of tungstacyclobutane also failed, but gave results which could be interpreted as mimicking metathesis. In spite of this apparent agreement, it is concluded that, if tungstacyclobutanes are actually formed, they are decomposed to tungstacarbene (alkylidenetungsten) and olefins rather than to tungstacyclopentanes, then to olefins. 相似文献
15.
A highly efficient and versatile method for the synthesis of various sphingolipids, such as sphingomyelin, ceramide, sphingosine, sphingosine 1-phosphate, and functionalized sphingosine derivatives, was established by two types of combinations of the olefin cross metathesis reaction. One reaction was between the same olefin part and appropriate amino alcohols, which were prepared starting from N-Boc-L-serine, and the other was between appropriate olefins and the same amino alcohol. [reaction: see text]. 相似文献
16.
The electrochemical reduction of WCl6 results in the formation of an active olefin (alkene) metathesis catalyst. The application of the WCl6–e?–Al–CH2Cl2 catalyst system to cross‐metathesis reactions of non‐functionalized acyclic olefins is reported. Undesirable reactions, such as double‐bond shift isomerization and subsequent metathesis, were not observed in these reactions. Cross‐metathesis of 7‐tetradecene with an equimolar amount of 4‐octene generated the desired cross‐product, 4‐undecene, in good yield. The reaction of 7‐tetradecene with 2‐octene, catalyzed by electrochemically reduced tungsten hexachloride, resulted in both self‐ and cross‐metathesis products. The cross‐metathesis products, 2‐nonene and 6‐tridecene, were formed in larger amounts than the self‐metathesis products of 2‐octene. The optimum catalyst/olefin ratio and reaction time were found to be 1 : 60 and 24 h, respectively. The cross‐metathesis of symmetrical olefins with α‐olefins was also studied under the predetermined conditions. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
17.
Yu Xie Ye Yuan Bibimaryam Mousavi Yuan Cai Cheng Kai Yin Lu Mehman Yusubov Francis Verpoort 《应用有机金属化学》2015,29(9):573-579
Olefin metathesis is a transition metal‐mediated transformation that rearranges the carbon atoms of the carbon–carbon double bond of olefins. This reaction has become one of the most important and powerful reactions. Therefore development of new, well‐defined, highly active and selective catalysts is very desirable and a valuable goal. This mini‐review mainly introduces the development of ruthenium catalysts in olefin metathesis highlighting oxygen‐chelated indenylidene ruthenium catalysts. Applying an alkoxyl group on the indenylidene ligand fragment can generate the Ru ? O chelating bond. Additionally, various modifications of the ligand as well as the catalytic activity for ring‐closing metathesis reaction and selectivity of cross metathesis reaction are overviewed. Finally, the perspectives on the development of new catalysts are summarized. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
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19.
Pd(II)‐Catalyzed CH Activation of Styrylindoles: Short,Efficient, and Regioselective Synthesis of Functionalized Carbazoles
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Rakesh K. Saunthwal Monika Patel Sonu Kumar Abhinandan K. Danodia Prof. Dr. Akhilesh K. Verma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(51):18601-18605
A novel PdII‐catalyzed approach for the direct synthesis of highly functionalized carbazoles from unprotected styrylindoles has been developed. The reaction features a variety of olefin substrates, which are readily switchable by subtle tuning of the reaction conditions. Investigations of the mechanism suggest that the C?H activation proceeds via enamine formation. 相似文献
20.
Dr. Johan Bidange Dr. Cédric Fischmeister Dr. Christian Bruneau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(35):12226-12244
Remarkable innovations have been made in the field of olefin metathesis due to the design and preparation of new catalysts. Ethenolysis, which is cross‐metathesis with ethylene, represents one catalytic transformation that has been used with the purpose of cleaving internal carbon–carbon double bonds. The objectives were either the ring opening of cyclic olefins to produce dienes or the shortening of unsaturated hydrocarbon chains to degrade polymers or generate valuable shorter terminal olefins in a controlled manner. This Review summarizes several aspects of this reaction: the catalysts, their degradation in the presence of ethylene, some parameters driving their productivity, the side reactions, and the applications of ethenolysis in organic synthesis and in potential industrial applications. 相似文献