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1.
The elementometalation process is a fundamental chemical step in several catalytic cycles. In this work, density functional theory computations have elucidated the detailed elementometalation mechanism of activated alkyne RCCR(RCO2Me) by Cp2TaH3 and rationalized the selectivity in experimental findings. The calculated results show that in the formation process of (E)-olefin monohydride((E)-Pro), the Gibbs free energy barrier is low and the entire reaction is spontaneous and exothermic; thus, (E)-Pro can be formed easily. The formation of (Z)-η2-olefin monohydride complex ((Z)-Pro) is difficult due to its high Gibbs free energy barrier. The formation process (E)-Pro consists of the following five steps: hydride H1-shift, conformational isomerism 1, hydride H2-shift, conformational isomerism 2, and olefin coordination process. Topological analysis shows that there is a five-membered ring plane structure in the reaction pathway and that the final product (E)-Pro belongs to a typical η2-olefin monohydride complex. Our calculated results provide an explanation for experimental observations and useful insights for further development of olefin functionalization. © 2019 Wiley Periodicals, Inc. 相似文献
2.
Stereoselective Preparation of Polyfunctional Alkenylindium(III) Halides and Their Cross‐Coupling with Unsaturated Halides 下载免费PDF全文
Zhi‐Liang Shen Prof. Dr. Paul Knochel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(19):7061-7065
The direct insertion of indium powder to cycloalkenyl iodides in the presence of LiCl in THF allows the preparation of new highly functionalized cycloalkenylindium(III) derivatives. In addition, we discovered that, in contrast to many metal insertions to alkenyl iodides which proceed with a loss of stereochemistry, the insertion of In/LiCl to stereodefined (Z)‐ and (E)‐styryl iodides in THF proceeded with high retention of stereochemistry. After a palladium‐catalyzed cross‐coupling, various polyfunctionalized (Z)‐ and (E)‐stilbenes were obtained with high stereoselectivity. 相似文献
3.
Daniel J. Tao Dr. Mikko Muuronen Yuriy Slutskyy Alexander Le Prof. Filipp Furche Prof. Larry E. Overman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(26):8786-8790
The stereochemical outcome of reactions of chiral nucleophilic trisubstituted acetonide radicals with electron‐deficient alkenes is dictated by a delicate balance between destabilizing non‐bonding interactions and stabilizing hydrogen‐bonding between substituents on the α and β carbons. 相似文献
4.
《Mendeleev Communications》2022,32(5):629-631
The Michael–Mannich cascade cyclization of cyano olefins, ethyl 4,4,4-trifluoro-3-oxobutanoate, aromatic aldehydes and ammonium acetate provides convenient stereoselective formation of ethyl 5,5-dicyano-4,6-diaryl-2-hydroxy-2-(trifluoromethyl)piperidine-3-carboxylates with fourstereogenic centers and dialkyl 4,6-diaryl-5-cyano-2-hydroxy-2-(trifluoromethyl)piperidine-3,5-dicarboxylates with five stereogenic centers. Ammonium acetate plays dual role, acting as a base and as a nitrogen source. 相似文献
5.
Haobing Wang Xia Wu Yang Yang Masayoshi Nishiura Zhaomin Hou 《Angewandte Chemie (International ed. in English)》2020,59(18):7173-7177
The precise control of monomer sequence and stereochemistry in copolymerization is of much interest and importance for the synthesis of functional polymers, but studies toward this goal have met with only limited success to date. Now, the co‐syndiospecific alternating copolymerization of methoxyphenyl‐ and N,N‐dimethylaminophenyl‐functionalized propylenes with styrene by half‐sandwich rare‐earth catalysts is reported. This reaction efficiently afforded the corresponding functionalized propylene‐alt‐styrene copolymers with a perfect alternating sequence and excellent co‐syndiotacticity (rrrr >99 %), thus constituting the first example of co‐stereospecific alternating copolymerization of polar and non‐polar olefins. 相似文献
6.
The insertion of an alkyne into transition metal–hydrogen bonds is a key elementary step in catalytic polymerization and hydrogenation processes. It was found that a (Z)- or (E)-type alkyenyl complex can be formed through trans/cis stereospecific processes. In this work, the reaction mechanism of Cp2M(L)H [Cp = η5-C5H5; M = Nb, V; L = CO, P (OMe)3] with dimethylacetylene dicarboxylate (DMAD), and the factors influencing the stereoselectivity have been investigated based on density functional theory calculations. The calculated results show that all of the reactions are exothermic. For L = CO, the Z-isomer product forms first even at low temperatures because of the low Gibbs free energy barrier (ΔG#). Then the Z-pro converts to E-pro , while for L = P (OMe)3, the exclusive product is the E-isomer. For different metal centers, the reaction mechanisms of the Cp2M(CO)H + DMAD (M = Nb and V) reaction are similar, while their products are different at room temperature. For M = Nb, because the energy barrier of the isomerization from Z-pro to E-pro is low and the relative free energies of Z-pro and E-pro are almost equal, both Z-pro and E-pro can be obtained. While for the Cp2V(CO)H + DMAD reaction, only the Z-pro can be obtained under mild conditions, E-pro can be obtained only at high temperatures. For the Cp2M(CO)H+DMAD(M=V and Nb) reactions, the formation of E-isomer products proceeds via two five-membered ring transition states. The calculated results provide an reasonable explanation for the experimental results and predict a new insertion reaction. 相似文献
7.
Dr. Yashapal Singh Prof. Dr. Alexei V. Demchenko 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(5):1042-1051
Following the recent discovery that traditional silver(I) oxide-promoted glycosidations of glycosyl bromides (Koenigs–Knorr reaction) can be greatly accelerated in the presence of catalytic TMSOTf, reported herein is a dedicated study of all major aspects of this reaction. A thorough investigation of numerous silver salts and careful refinement of the reaction conditions led to an improved mechanistic understanding. This, in turn, led to a significant reduction in the amount of silver salt required for these glycosylations. The progress of this reaction can be monitored by naked eye, and the completion of the reaction can be judged by the disappearance of characteristic dark color of Ag2O. Further evidence on higher reactivity of benzoylated α-bromides in comparison to that of their benzylated counterparts has been acquired. 相似文献
8.
Manas Das Dr. Atul Manvar Dr. Maïwenn Jacolot Dr. Marco Blangetti Dr. Roderick C. Jones Prof. Dr. Donal F. O'Shea 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(24):8737-8740
The synthesis of bench‐stable α,α‐bis(trimethylsilyl)toluenes and tris(trimethylsilyl)methane is described and their use in stereoselective Peterson olefinations has been achieved with a wide substrate scope. Product stereoselectivity was poor with carbonyl electrophiles (E/Z ~1:1 to 4:1) though this was significantly improved by employing the corresponding substituted N‐benzylideneaniline (up to 99:1) as an alternative electrophile. The olefination byproduct was identified as N,N‐bis(trimethylsilyl)aniline and could be easily separated from product by aqueous acid extraction. Evidence for an autocatalytic cycle has been obtained. 相似文献
9.
Inside Cover: Palladium/Zinc Co‐Catalyzed syn‐Stereoselectively Asymmetric Ring‐Opening Reaction of Oxabenzonorbornadienes with Phenols (Chem. Eur. J. 25/2015) 下载免费PDF全文
10.
Dr. Elizabeth H. Krenske Sarah Lam Jerome P. L. Ng Brian Lo Dr. Sze Kui Lam Prof. Dr. Pauline Chiu Prof. Dr. Kendall N. Houk 《Angewandte Chemie (International ed. in English)》2015,54(25):7422-7425
Silyl‐triflate‐catalyzed (4+3) cycloadditions of epoxy enolsilanes with dienes provide a mild and chemoselective synthetic route to seven‐membered carbocycles. Epoxy enolsilanes containing a terminal enolsilane and a single stereocenter undergo cycloaddition with almost complete conservation of enantiomeric purity, a finding that argues against the involvement of oxyallyl cation intermediates which have been previously proposed for these types of reactions. Reported are theoretical and experimental investigations of the cycloaddition mechanism. The major enantiomers of the cycloadducts are derived from SN2‐like reactions of the silylated epoxide with the diene, in which stereospecific ring opening and formation of the two new C? C bonds occur in a single step. Calculations predict, and experiments confirm, that the observed small losses of enantiomeric purity are traced to a triflate‐mediated double SN2 cycloaddition pathway. 相似文献