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1.
We have developed a ligand that reversibly binds to aniline substrates, allowing for the control of regioselectivity and enantioselectivity in hydroformylation. In this paper we address how the electronics of the aniline ring affect both the binding of the substrate to the ligand and the enantioselectivity in this reaction. 相似文献
2.
[formula: see text] The asymmetric synthesis of beta-hydroxy-alpha-amino acids is reported which relies on the use of alpha,beta-unsaturated aryl ester substrates and the dihydroquinyl alkaloid ligand system (DHQ)2-AQN to control the regio- and enantioselectivity of the asymmetric aminohydroxylation (AA) process. alpha,beta-Unsaturated ester substrates of type 1 have a significant effect on the substrate-ligand recognition event which results in a reversal of regioselectivity in the AA reaction. 相似文献
3.
Toledo L Masgrau L Lluch JM González-Lafont À 《Journal of computer-aided molecular design》2011,25(9):825-835
Lipoxygenases (LOs) are implicated in the regulation of metabolic processes and in several human diseases. Revealing their
exact role is hindered by an incomplete understanding of their activity, including substrate specificity and substrate alignment
in the active site. Recently, it has been proposed that the change in substrate specificity for arachidonic acid (AA) or linoleic
acid (LA) could be part of an auto-regulatory mechanism related to cancer grow. Kinetic differences between reactions of 15-hLO
with AA and LA have also led to the suggestion that the two substrates could present mechanistic differences. In the absence
of a crystal structure for the substrate:15-LO complex, here we present an atomic-level study of catalytically competent binding
modes for LA to rabbit 15-LO (15-rLO-1) and compare the results to our previous work on AA. Docking calculations, molecular
dynamics simulations, re-docking and cross-docking calculations are all used to analyze the differences and similarities between
the binding modes of the two substrates. Interestingly, LA seems to adapt more easily to the enzyme structure and differs
from AA on some dynamical aspects that could introduce kinetic differences, as observed experimentally. Still, our study concludes
that, despite the different chain lengths and number of insaturations between these two physiological substrates of 15-rLO-1,
the enzyme seems to catalyze their hydroperoxidation by binding them with a common binding mode that leads to similar catalytically
competent complexes. 相似文献
4.
[reaction: see text] The pH-controlled Sharpless asymmetric aminohydroxylation (AA) of styrenes provides 1-aryl-2-amino ethanols (regioisomer B) with high enantio-, chemo-, and regioselectivity. As existing AA protocols typically give regioisomer A as the major reaction product when using carbamate nitrogen sources, this method is a convenient alternative for the selective production of regioisomer B. 相似文献
5.
In situ Generated Ruthenium Catalyst Systems Bearing Diverse N‐Heterocyclic Carbene Precursors for Atom‐Economic Amide Synthesis from Alcohols and Amines
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Dr. Hua Cheng Mao‐Qian Xiong Chuan‐Xiang Cheng Hua‐Jing Wang Qiang Lu Hong‐Fu Liu Fu‐Bin Yao Dr. Cheng Chen Prof. Dr. Francis Verpoort 《化学:亚洲杂志》2018,13(4):440-448
The transition‐metal‐catalyzed direct synthesis of amides from alcohols and amines is herein demonstrated as a highly environmentally benign and atom‐economic process. Among various catalyst systems, in situ generated N‐heterocyclic carbene (NHC)‐based ruthenium (Ru) halide catalyst systems have been proven to be active for this transformation. However, these existing catalyst systems usually require an additional ligand to achieve satisfactory results. In this work, through extensive screening of a diverse variety of NHC precursors, we discovered an active in situ catalyst system for efficient amide synthesis without any additional ligand. Notably, this catalyst system was found to be insensitive to the electronic effects of the substrates, and various electron‐deficient substrates, which were not highly reactive with our previous catalyst systems, could be employed to afford the corresponding amides efficiently. Furthermore, mechanistic investigations were performed to provide a rationale for the high activity of the optimized catalyst system. NMR‐scale reactions indicated that the rapid formation of a Ru hydride intermediate (signal at δ=?7.8 ppm in the 1H NMR spectrum) after the addition of the alcohol substrate should be pivotal in establishing the high catalyst activity. Besides, HRMS analysis provided possible structures of the in situ generated catalyst system. 相似文献
6.
Peter Fristrup 《Journal of organometallic chemistry》2006,691(10):2182-2198
The interactions between the substrate and the ligand in the Sharpless AD reaction have been examined in detail, using a combination of substrate competition experiments and molecular modeling of transition states. There is a good agreement between computational and experimental results, in particular for the stereoselectivity of the reaction. The influence of each moiety in the second-generation ligand (DHQD)2PHAL on the rate and selectivity of the reaction has been elucidated in detail. 相似文献
7.
8.
Shao‐Tao Bai Charles B. Bheeter Joost N. H. Reek 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(37):13173-13177
Reported is an iridium catalyst for ortho‐selective C?H borylation of challenging secondary aromatic amide substrates, and the regioselectivity is controlled by hydrogen‐bond interactions. The BAIPy ‐Ir catalyst forms three hydrogen bonds with the substrate during the crucial activation step, and allows ortho‐C?H borylation with high selectivity. The catalyst displays unprecedented ortho selectivities for a wide variety of substrates that differ in electronic and steric properties, and the catalyst tolerates various functional groups. The regioselective C?H borylation catalyst is readily accessible and converts substrates on gram scale with high selectivity and conversion. 相似文献
9.
Jurjen Meeuwissen Mark Kuil Dr. Alida M. van der Burg Albertus J. Sandee Dr. Joost N. H. Reek Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(39):10272-10279
A procedure is described for the automated screening and lead optimization of a supramolecular‐ligand library for the rhodium‐catalyzed asymmetric hydrogenation of five challenging substrates relevant to industry. Each catalyst is (self‐) assembled from two urea‐functionalized ligands and a transition‐metal center through hydrogen‐bonding interactions. The modular ligand structure consists of three distinctive fragments: the urea binding motif, the spacer, and the ligand backbone, which carries the phosphorus donor atom. The building blocks for the ligand synthesis are widely available on a commercial basis, thus enabling access to a large number of ligands of high structural diversity. The simple synthetic steps enabled the scale‐up of the ligand synthesis to multigram quantities. For the catalyst screening, a library of twelve new chiral ligands was prepared that comprised substantial variation in electronic and steric properties. The automated procedures employed ensured the fast catalyst assembly, screening, and direct acquisition of samples for analysis. It appeared that the most selective catalyst was different for every substrate investigated and that small variations in the building blocks had a major impact on the catalyst performance. For two substrates, a catalyst was found that provided the product with outstanding enantioselectivity. The subsequent automated optimization of these two leads showed that an increase of catalyst loading, dihydrogen pressure, and temperature had a positive effect on the catalyst activity without affecting the catalyst selectivity. 相似文献
10.
Reaction of symmetrical and unsymmetrical alkynes with arylboronic acids, using PdCl2 as catalyst source and i-Pr2NPPh2 as ligand, afforded trisubstituted alkenes with regioselectivity in good to excellent yields without a common additional acetic acid. Its efficiency has been demonstrated by its good functional groups, high yield and crowded substrates. 相似文献
11.
Chloro-(eta6-arene) complexes of ruthenium(II) with N-sulfonyl-1,2-ethylenediamine ligands that have one or two styrene side chains have been synthesised and characterised. The chloro ligand was substituted with a diphenylphosphinato ligand and the resulting organometallic complexes are transition state analogues for the ruthenium-catalysed transfer hydrogenation of benzophenone. Following the protocol of molecular imprinting, these complexes were copolymerised with ethylene glycol dimethacrylate (EGDMA) in the presence of a porogen. The polymers were ground and sieved, and the phosphinato ligand was substituted with a chloro ligand, thus generating a shape-selective cavity in close proximity to the catalytically active metal centre. When tested for their ability to catalyse the reduction of benzophenone, the imprinted polymers showed a significantly higher activity (up to a factor of seven) than control polymers without cavities. Out of a mixture of seven different aromatic and aliphatic ketones, benzophenone was preferentially reduced when the imprinted polymer was used. Furthermore, the specificity of the catalyst for diaryl ketones has been confirmed in a reaction with a bifunctional substrate, 4-acetyl-benzophenone; the diaryl ketone was reduced faster with the imprinted catalyst than the acetyl group. The opposite regioselectivity was observed with the control polymer. Both the activity and the selectivity of the imprinted catalysts are dependent on how the ruthenium complexes are attached to the polymer backbone. A double connection proved to give superior results. 相似文献
12.
Moritz Voss Dr. Sumire Honda Malca Prof. Dr. Rebecca Buller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(33):7336-7345
Freestanding Fe/α-ketoglutarate-dependent halogenases are oxidoreductases that catalyze the installation of halogen atoms into unactivated sp3-hybridized carbon centers with high stereo- and regioselectivity. Since their discovery in 2014, a small number of indole alkaloid and amino acid halogenases have been identified and characterized. First enzyme engineering examples suggest that the accessible substrate range of these enzymes may be expanded through the use of rational enzyme design and directed evolution. Structural investigations of non-heme iron halogenases acting on freestanding as well as tethered substrates are beginning to inform about the principles of the underlying halogenation mechanism. 相似文献
13.
14.
Ichinose M Suematsu H Yasutomi Y Nishioka Y Uchida T Katsuki T 《Angewandte Chemie (International ed. in English)》2011,50(42):9884-9887
'Salen' along: The iridium(III)-salen complex 1 efficiently catalyzes the title reaction of 2-ethylbenzenesulfonyl azides to give five-membered sultams with high enantioselectivity. Other 2-alkyl-substitued substrates lead to five- and six-membered sultams with high enantioselectivity; the regioselectivity depends upon the substrate and the catalyst used. EDG=electron-donating group. 相似文献
15.
Pim R. Linnebank Stephan Falcão Ferreira Alexander M. Kluwer Prof. Dr. Joost N. H. Reek 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(37):8214-8219
Regioselective catalytic transformations using supramolecular directing groups are increasingly popular as it allows for control over challenging reactions that may otherwise be impossible. In most examples the reactive group and the directing group are close to each other and/or the linker between the directing group is very rigid. Achieving control over the regioselectivity using a remote directing group with a flexible linker is significantly more challenging due to the large conformational freedom of such substrates. Herein, we report the redesign of a supramolecular Rh–bisphosphite hydroformylation catalyst containing a neutral carboxylate receptor (DIM pocket) with a larger distance between the phosphite metal binding moieties and the DIM pocket. For the first time regioselective conversion of internal and terminal alkenes containing a remote carboxylate directing group is demonstrated. For carboxylate substrates that possess an internal double bond at the Δ-9 position regioselectivity is observed. As such, the catalyst was used to hydroformylate natural monounsaturated fatty acids (MUFAs) in a regioselective fashion, forming of an excess of the 10-formyl product (10-formyl/9-formyl product ratio of 2.51), which is the first report of a regioselective hydroformylation reaction of such substrates. 相似文献
16.
Chikkali SH Bellini R de Bruin B van der Vlugt JI Reek JN 《Journal of the American Chemical Society》2012,134(15):6607-6616
A small family of new chiral hybrid, diphosphorus ligands, consisting of phosphine-phosphoramidites L1 and L2 and phosphine-phosphonites L3a-c, was synthesized for the application in Rh-catalyzed asymmetric hydroformylation of heterocyclic olefins. High-pressure (HP)-NMR and HP-IR spectroscopy under 5-10 bar of syngas has been employed to characterize the corresponding catalyst resting state with each ligand. Indole-based ligands L1 and L2 led to selective ea coordination, while the xanthene derived system L3c gave predominant ee coordination. Application of the small bite-angle ligands L1 and L2 in the highly selective asymmetric hydroformylation (AHF) of the challenging substrate 2,3-dihydrofuran (1) yielded the 2-carbaldehyde (3) as the major regioisomer in up to 68% yield (with ligand L2) along with good ee's of up to 62%. This is the first example in which the asymmetric hydroformylation of 1 is both regio- and enantioselective for isomer 3. Interestingly, use of ligand L3c in the same reaction completely changed the regioselectivity to 3-carbaldehyde (4) with a remarkably high enantioselectivity of 91%. Ligand L3c also performs very well in the Rh-catalyzed asymmetric hydroformylation of other heterocyclic olefins. Highly enantioselective conversion of the notoriously difficult substrate 2,5-dihydrofuran (2) is achieved using the same catalyst, with up to 91% ee, concomitant with complete regioselectivity to the 3-carbaldehyde product (4) under mild reaction conditions. Interestingly, the Rh-catalyst derived from L3c is thus able to produce both enantiomers of 3-carbaldehyde 4, simply by changing the substrate from 1 to 2. Furthermore, 85% ee was obtained in the hydroformylation of N-acetyl-3-pyrroline (5) with exceptionally high regioselectivities for 3-carbaldehyde 8Ac (>99%). Similarly, an ee of 86% for derivative 8Boc was accomplished using the same catalyst system in the AHF of N-(tert-butoxycarbonyl)-3-pyrroline (6). These results represent the highest ee's reported to date in the AHF of dihydrofurans (1, 2) and 3-pyrrolines (5, 6). 相似文献
17.
Dr. Debasis Banerjee Dr. Kathrin Junge Prof. Dr. Matthias Beller 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(6):1656-1661
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
18.
Drug Metabolism by Cytochrome P450 Enzymes: What Distinguishes the Pathways Leading to Substrate Hydroxylation Over Desaturation?
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Dr. Li Ji Abayomi S. Faponle Dr. Matthew G. Quesne Mala A. Sainna Jing Zhang Dr. Alicja Franke Dr. Devesh Kumar Prof. Dr. Rudi van Eldik Prof. Dr. Weiping Liu Dr. Sam P. de Visser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(25):9083-9092
Cytochrome P450 enzymes are highly versatile biological catalysts in our body that react with a broad range of substrates. Key functions in the liver include the metabolism of drugs and xenobiotics. One particular metabolic pathway that is poorly understood relates to the P450 activation of aliphatic groups leading to either hydroxylation or desaturation pathways. A DFT and QM/MM study has been carried out on the factors that determine the regioselectivity of aliphatic hydroxylation over desaturation of compounds by P450 isozymes. The calculations establish multistate reactivity patterns, whereby the product distributions differ on each of the spin‐state surfaces; hence spin‐selective product formation was found. The electronic and thermochemical factors that determine the bifurcation pathways were analysed and a model that predicts the regioselectivity of aliphatic hydroxylation over desaturation pathways was established from valence bond and molecular orbital theories. Thus, the difference in energy of the O?H versus the O?C bond formed and the π‐conjugation energy determines the degree of desaturation products. In addition, environmental effects of the substrate binding pocket that affect the regioselectivities were identified. These studies imply that bioengineering P450 isozymes for desaturation reactions will have to include modifications in the substrate binding pocket to restrict the hydroxylation rebound reaction. 相似文献
19.
Polymers such as poly(ethylene glycol) (PEG) have proven use in a variety of applications including organic synthesis. We now disclose our investigations into the recently disputed report that PEG tartrate esters can reverse the enantioselectivity of the Sharpless asymmetric epoxidation reaction. The results presented herein have clarified that the enantioselectivity of this reaction can be reproducibly reversed solely as a function of the molecular weight of the appended PEG. By preparing a range of tartrate ligands with varying PEG chains lengths, the reversal was found to occur within a molecular weight change of only 800. As the PEG chain did not affect the inherent chirality of the ligand, the enantioreversal was proposed to occur as a result of two Ti-ligand complexes which differ in their molecularity of ligand, one monomeric in ligand and the other dimeric. Support for this hypothesis was given through equilibrium measurements which revealed that the predominant species in Ti/PEG tartrate ester mixtures is a distinct 2:1 Ti-ligand complex, as opposed to the 2:2 Ti-ligand complex of traditional Sharpless asymmetric epoxidations. In total, these data represent an unrecognized property of PEG-supported catalysts that could open up new venues in the control of asymmetric reactions by means of achiral appended polymers. 相似文献
20.
A General Catalytic Hydroamidation of 1,3‐Dienes: Atom‐Efficient Synthesis of N‐Allyl Heterocycles,Amides, and Sulfonamides
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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