共查询到20条相似文献,搜索用时 31 毫秒
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Pierre‐Alain R. Breuil Frederic W. Patureau Joost N. H. Reek Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(12):2162-2165
H bonds make the catalysts! A single hydrogen bond between ligands coordinated to a rhodium center is critical for the formation of pure supramolecular catalysts for asymmetric hydrogenation reactions. The ester group of the amidite ligand (see scheme) also forms a hydrogen bond with the coordinated substrate. Use of the heterocomplex afforded the highest enantioselectivity reported to date for the hydrogenation of several ester substrates.
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Stephanie Ganss Prof. Dr. Bernhard Breit 《Angewandte Chemie (International ed. in English)》2016,55(33):9738-9742
A highly attractive route toward macrolactones, which form the cyclic scaffold of a multitude of diverse natural compounds, is described. Although many chemical approaches to this structural motif have been explored, an asymmetric variant of the cyclization is unprecedented. Herein we present an enantioselective macrolactonization through an intramolecular atom‐economical rhodium‐catalyzed coupling of ω‐allenyl‐substituted carboxylic acids. The use of a modified diop ligand, chiral DTBM‐diop, led to high enantioselectivity (up to 93 % ee). The reaction tolerated a large variety of functionalities, including α,β‐unsaturated carboxylic acids and depsipeptides, and provided the desired macrocycles with very high enantio‐ and diastereoselectivity. 相似文献
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Iridium‐Catalyzed Enantioselective Hydrogenation of Oxocarbenium Ions: A Case of Ionic Hydrogenation
Tilong Yang Yongjie Sun Heng Wang Zhenyang Lin Jialin Wen Xumu Zhang 《Angewandte Chemie (International ed. in English)》2020,59(15):6108-6114
Ionic hydrogenation has not been extensively explored, but is advantageous for challenging substrates such as unsaturated intermediates. Reported here is an iridium‐catalyzed hydrogenation of oxocarbenium ions to afford chiral isochromans with high enantioselectivities. A variety of functionalities are compatible with this catalytic system. In the presence of a catalytic amount of the Brønsted acid HCl, an α‐chloroether is generated in situ and subsequentially reduced. Kinetic studies suggest first‐order kinetics in the substrate and half‐order kinetics in the catalyst. A positive nonlinear effect, together with the half kinetic order, revealed a dimerization of the catalyst. Possible reaction pathways based on the monomeric iridium catalyst were proposed and DFT computational studies revealed an ionic hydrogenation pathway. Chloride abstraction and the cleavage of dihydrogen occur in the same step. 相似文献
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Chiral guanidines have been widely used as Brønsted base catalysts and phase transfer catalysts in enantioselective reactions. Due to their amendable structure and powerful catalytic ability, they have attracted much interest. Several new catalysts containing a guanidinium moiety have been reported over the past decade and many promising outcomes have been achieved. This article illustrates the progress of chiral guanidine catalysis in asymmetric synthesis from 2009 to 2018. It is an update of a review of the same title published in 2009. 相似文献
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Pinches like a crab : The utilization of guanidines as catalysts has been growing at a steady pace. They possess high pKa values and activate through dual hydrogen‐bonding modes of activation. This Focus Review highlights the development of chiral guanidine catalysts in asymmetric organic transformations.
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A Readily Accessible Class of Chiral Cp Ligands and their Application in RuII‐Catalyzed Enantioselective Syntheses of Dihydrobenzoindoles 下载免费PDF全文
Dr. Shou‐Guo Wang Sung Hwan Park Prof. Dr. Nicolai Cramer 《Angewandte Chemie (International ed. in English)》2018,57(19):5459-5462
Chiral cyclopentadienyl (Cpx) ligands have a large application potential in enantioselective transition‐metal catalysis. However, the development of concise and practical routes to such ligands remains in its infancy. We present a convenient and efficient two‐step synthesis of a novel class of chiral Cpx ligands with tunable steric properties that can be readily used for complexation, giving CpxRhI, CpxIrI, and CpxRuII complexes. The potential of this ligand class is demonstrated with the latter in the enantioselective cyclization of azabenzonorbornadienes with alkynes, affording dihydrobenzoindoles in up to 98:2 e.r., significantly outperforming existing binaphthyl‐derived Cpx ligands. 相似文献
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Highly Enantioselective Rhodium‐Catalyzed Addition of Arylboroxines to Simple Aryl Ketones: Efficient Synthesis of Escitalopram 下载免费PDF全文
Linwei Huang Jinbin Zhu Guangjun Jiao Dr. Zheng Wang Prof. Dr. Xingxin Yu Prof. Dr. Wei‐Ping Deng Prof. Dr. Wenjun Tang 《Angewandte Chemie (International ed. in English)》2016,55(14):4527-4531
Highly enantioselective additions of arylboroxines to simple aryl ketones have been achieved for the first time with a Rh/(R,R,R,R)‐WingPhos catalyst, thus providing a range of chiral diaryl alkyl carbinols with excellent ee values and yields. (R,R,R,R)‐WingPhos has been proven to be crucial for the high reactivity and enantioselectivity. The method has enabled a new, concise, and enantioselective synthesis of the antidepressant drug escitalopram. 相似文献
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Palladium‐Catalyzed Enantioselective Reductive Heck Reactions: Convenient Access to 3,3‐Disubstituted 2,3‐Dihydrobenzofuran 下载免费PDF全文
Zhan‐Ming Zhang Bing Xu Yanyan Qian Lizuo Wu Yuanqi Wu Lujia Zhou Prof. Dr. Yu Liu Prof. Dr. Junliang Zhang 《Angewandte Chemie (International ed. in English)》2018,57(32):10373-10377
The first example of highly enantioselective intramolecular hydroarylation of allyl aryl ethers was realized by palladium‐catalyzed reductive heck reactions utilizing a new chiral sulfinamide phosphine ligand (N‐Me‐ XuPhos ). N‐Me‐ XuPhos can be easily prepared on gram scale from readily available starting materials in a one‐pot synthesis approach. A series of optically active 2,3‐dihydrobenzofurans bearing a quaternary stereocenter were obtained in good yields and with excellent enantioselectivities. The practicality of this reaction was validated in the straightforward synthesis of CB2 receptor agonists. Moreover, deuterium was efficiently incorporated into the products. 相似文献
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Construction of a Chiral Silicon Center by Rhodium‐Catalyzed Enantioselective Intramolecular Hydrosilylation 下载免费PDF全文
Dr. Yuki Naganawa Tomoya Namba Mayu Kawagishi Prof. Dr. Hisao Nishiyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(26):9319-9322
Rhodium‐catalyzed enantioselective desymmetrizing intramolecular hydrosilylation of symmetrically disubstituted hydrosilanes is described. The original axially chiral phenanthroline ligand (S)‐BinThro (Binol‐derived phenanthroline) was found to work as an effective chiral catalyst for this transformation. A chiral silicon stereogenic center is one of the chiral motifs gaining much attention in asymmetric syntheses and the present protocol provides cyclic five‐membered organosilanes incorporating chiral silicon centers with high enantioselectivities (up to 91 % ee). The putative active RhI catalyst takes the form of an N,N,O‐tridentate coordination complex, as determined by several complementary experiments. 相似文献
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Dr. Zhiyao Zheng Yuxi Cao Prof. Dongsheng Zhu Dr. Zheng Wang Prof. Kuiling Ding 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(40):9491-9497
A series of 1,1′-spirobiindane-7,7′-diol ( SPINOL ) analogues bearing a 2,2′-dimethyl-, cyclopentyl-, or cyclohexyl-fused ring were synthesized, and their distinct structural features were elucidated by X-ray crystallography. On the basis of these scaffolds, chiral monophosphoramidite ligands 6 a – m were synthesized, which demonstrated excellent enantioselectivity in RhI-catalyzed asymmetric hydrogenation of a dehydro amino acid methyl ester. Ligands 6 a – m were also successfully applied in the RhI-catalyzed enantioselective [4+2] cycloaddition of α,β-unsaturated imines with isocyanates, which afforded the corresponding pyrimidinones in good yields (60–92 %) with high enantioselectivities (75–92 % ee). 相似文献
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Ernest Salomó Dr. Sílvia Orgué Prof. Antoni Riera Prof. Xavier Verdaguer 《Angewandte Chemie (International ed. in English)》2016,55(28):7988-7992
The MaxPHOX–Ir catalyst system provided the highest selectivity ever reported for the reduction of cyclic enamides derived from α‐ and β‐tetralones. This result indicates that iridium catalysts are also proficient in reducing alkenes bearing metal‐coordinating groups. In the present system, selectivity was pressure‐dependent: In most cases, a decrease in the H2 pressure to 3 bar resulted in an increase in enantioselectivity. Moreover, the process can be carried out in environmentally friendly solvents, such as methanol and ethyl acetate, with no loss of selectivity. 相似文献
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Pengxiang Zhang Dr. Jipan Yu Fei Peng Xudong Wu Jiyang Jie Can Liu Hua Tian Dr. Haijun Yang Prof. Dr. Hua Fu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17477-17484
A new type of axially chiral cyclo‐[1,1′‐biphenyl]‐2,2′‐diol (CYCNOL) ligands with adjustable dihedral angles have been developed by varying the bridge chain length. Eight‐, nine‐ and ten‐membered cyclo‐ligands were prepared and evaluated by using two representative examples: enantioselective additions of diethylzinc to aldehydes and organometallic reagents to enones. The results revealed that the fine regulation of dihedral angles through variation of the bridge chain length was effective in the asymmetric synthesis. 相似文献
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Design and Assembly of a Chiral Metallosalen‐Based Octahedral Coordination Cage for Supramolecular Asymmetric Catalysis 下载免费PDF全文
Chunxia Tan Jingjing Jiao Zijian Li Prof. Yan Liu Xing Han Prof. Yong Cui 《Angewandte Chemie (International ed. in English)》2018,57(8):2085-2090
Supramolecular containers featuring both high catalytic activity and high enantioselectivity represent a design challenge of practical importance. Herein, it is demonstrated that a chiral octahedral coordination cage can be constructed by using twelve enantiopure Mn(salen)‐derived dicarboxylic acids as linear linkers and six Zn4‐p‐tert‐butylsulfonylcalix[4]arene clusters as tetravalent four‐connected vertices. The porous cage features a large hydrophobic cavity (≈3944 Å3) decorated with catalytically active metallosalen species and is shown to be an efficient and recyclable asymmetric catalyst for the oxidative kinetic resolution of racemic secondary alcohols and the epoxidation of olefins with up to >99 % enantiomeric excess. The cage architecture not only prevents intermolecular deactivation and stabilizes the Mn(salen) catalysts but also encapsulates substrates and concentrates reactants in the cavity, resulting in enhanced reactivity and enantioselectivity relative to the free metallosalen catalyst. 相似文献