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A Pd-catalyzed formal [5 + 3] intermolecular cycloaddition reaction of isatin-derived alpha-(trifluoromethyl)imines with aryl substituted vinylethylene carbonates (VECs) has been reported, affording trifluoromethyl-group-containing spirooxindoles fused with an eight-membered ring as a single diastereoisomer in good yields in the presence of a Br°nsted acid in a one-pot manner under mild conditions. The asymmetric version of this reaction has been also realized using a chiral phosphine ligand along with the further transformation of the obtained product to give a spirooxindolo pyrrolidine derivative upon oxidation.

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Chiral Catalysts,
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This work details a study whereby the characterization of chiral selectors and identification of optimal separation conditions is evaluated by steady-state fluorescence anisotropy measurements. Earlier studies in our laboratory have shown fluorescence anisotropy to be an effective tool in evaluating chiral recognition, and in this study, the feasibility of characterizing chiral separation systems by the technique is evaluated. Four chiral selectors were examined under various conditions to explore correlation between chiral separation ability and differences in the steady-state fluorescence anisotropy of the enantiomers measured under similar conditions. A good correlation between the fluorescence anisotropy data and separation data was observed with R 2 values ranging from 0.9279 to 0.9959. The fluorescence anisotropy measurements were examined under conditions that mimicked chiral separation conditions and the feasibility of a priori optimization of chiral separations is discussed.

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Chiral Catalysts,
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Pictet-Spengler reactions are extensively utilized in the synthesis of various indole alkaloids. However, their mechanisms have been a controversial research topic. The role of spiroindolenine, the generally proposed key intermediate in catalytic asymmetric Pictet-Spengler reactions, remains elusive. Herein, combined density functional theory calculations and direct molecular dynamics simulations reveal that the role of this intermediate is divergent. The spiroindolenine acts as either a productive or a non-productive intermediate depending on the shape of the potential energy surface. In the former case, dynamic effects play an important role in the rearrangement of spiroindolenine, which can occur without passing through the intervening transition states along the reaction coordinates. In the latter case, the formation of spiroindolenine is only an off-cycle equilibrium. These theoretical predictions were verified experimentally. Furthermore, these insights were applied to seven reported catalytic asymmetric Pictet-Spengler reactions, leading to unified mechanistic understandings of this synthetically enabling reaction. The unique charm of synthetic chemistry stems from its room for creativity in breaking and constructing chemical bonds. Developing novel synthetic methodologies is the central task of fundamental organic chemistry, which can facilitate or enable access to valuable classes of compounds or materials. The Pictet-Spengler reaction is a key method for the synthesis of indole-derived natural products, an important class of compounds in drug discovery. Rational design of new chemical reactivity largely relies on deep mechanistic understandings. However, because of the inherent complexity of systems on the molecular level, usually a reaction mechanism can be perturbed by subtle changes of single reaction parameters. Hence, pursuing unified mechanistic understandings of synthetically enabling reactions is of great significance academically and can pave the way for crucial industrial synthetic applications in various fields. Pictet-Spengler reactions have widely been employed in the synthesis of polycyclic-indole-derived natural products. However, the mechanism of this reaction has remained as a controversial research topic. In this article, You and co-workers performed combined density functional theory calculations and direct molecular dynamics simulations to provide unified mechanistic understandings of Pictet-Spengler reactions with an emphasis on the divergent role played by spiroindolenine intermediates. The key theoretical predictions are well supported by further experiments.

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The organocatalytic dearomative [4 + 2] cycloadditions of biomass-derived 2,5-dimethylfuran with ortho-quinone methides were developed, affording two diffferent types of multisubstituted chromanes in high yields and excellent diastereoselectivities. The controllable synthesis of these two types of multisubstituted chromanes could be achieved by succinctly varying the reaction conditions.

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The first enantioselective organocatalytic intramolecular Morita-Baylis-Hillman (MBH) reaction of sterically highly demanding beta,beta-disubstituted enones is presented. The MBH reaction of beta,beta-disubstituted-alpha,beta-unsaturated electron-withdrawing systems was previously considered to be unfeasible. Towards this end, designer substrates, which under simple and practical reaction conditions generate a variety of cyclopenta[b]annulated arenes and heteroarenes in excellent enantiopurities and near-quantitative yields in remarkably short reaction times, are described. The reason for the unusually facile nature of this reaction is attributed to the synergy guided and entropically favored intramolecular reaction. Further, this strategy provides easy access to a substantial number of bioactive natural products and pharmaceutically significant compounds.

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Chiral Catalysts,
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An efficient and novel rhodium-catalyzed formal C-O insertion reaction of alkyne-tethered diazo compounds for the synthesis of 3H-indol-3-ols is described. A type of donor/donor rhodium carbene generated in situ via a carbene/alkyne metathesis (CAM) process is the key intermediate and terminates in a unique transformation different from donor/acceptor carbenoids. In addition, 18O-labeling experiments indicate that intramolecular oxygen-atom transfer from the amide group to the carbon-carbon triple bond occurs during this transformation.

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Reference:
Chiral Catalysts,
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A highly diastereo- and enantioselective four-component reaction of a diazo ketone with two molecules of anilines and ethyl glyoxylate was achieved under Rh2(OAc)4 and chiral phosphoric acid cocatalyzed conditions. This transformation proceeds through a Mannich-type trapping of the ammonium ylide generated from metal carbene and one molecule of aniline with iminoester derived from another molecule of aniline and ethyl glyoxylate. With this method, a series of chiral alpha,beta-diamino acid derivatives were efficiently constructed in good yields and with good to excellent diastereo- and enantioselectivities. Georg Thieme Verlag Stuttgart New York.

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The design of a synergistic rhodium(II) carboxylate and BINOL phosphoric acid catalyzed efficient multicomponent reaction of enaldiazo compounds, arylamines, and aryl aldehydes leading to the first transition-metal-catalyzed direct synthesis of valuable alpha-pyrrolylbenzylamines is disclosed. The reaction is proposed to involve a transient ammonium ylide of a new class of electrophilic rhodium enalcarbenoid, its regioselective Mannich reaction, and a cyclocondensation cascade. The methodology was used in a highly diastereoselective synthesis of a binaphthyl based chiral pyrrole.

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Chiral Catalysts,
Chiral catalysts – SlideShare

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Reaction trio: The title reaction delivers Ci£H functionalized pyrrole derivatives in moderate to good yields. This novel three-component reaction provides both syn- and anti-pyrrole derivatives having two contiguous stereocenters with good regio-, diastereo-, and enantioselectivity. This process represents the first highly enantioselective palladium-carbenoid-mediated reaction.

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Application In Synthesis of (R)-4-Hydroxydinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide. In my other articles, you can also check out more blogs about 39648-67-4

Reference:
Chiral Catalysts,
Chiral catalysts – SlideShare

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.39648-67-4, Name is (R)-4-Hydroxydinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide, molecular formula is C20H13O4P. In a Article,once mentioned of 39648-67-4, category: chiral-catalyst

A rapid construction of the tetracyclic core (±)-2 of (±)-cycloclavine (1) was accomplished in seven steps and 24% overall yield from commercially available aldehyde 7. Key features include a domino Friedel-Crafts/nitro-Michael reaction to construct the C ring and an intramolecular ammonolysis of a diester to close the D ring. In addition, a versatile 4-amino Uhle’s ketone (±)-3 was afforded rapidly in five steps and 43% overall yield.

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Reference:
Chiral Catalysts,
Chiral catalysts – SlideShare