Dynamic parallel kinetic resolution of α-ferrocenyl cation initiated by chiral Brønsted acid catalyst

Toda, Yasunori; Korenaga, Takashi; Obayashi, Ren; Kikuchi, Jun; Terada, Masahiro

doi:10.1039/d1sc02122b

Cited by 9 publications

(2 citation statements)

References 57 publications

(22 reference statements)

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“…In fact, shortly after the initial synthesis of vinylferrocene by Arimoto and Haven in 1955, [2] its remarkable ability to undergo uncatalyzed addition reactions with weak acids, such as hydrogen azide or acetic acid, was demonstrated. [3] Following these pioneering findings, various regioselective 1,2-hydrofunctionalization reactions involving HX reagents were reported, encompassing hydrohalogenation, [4] hydroamination, [5] hydrosilylation, [6] hydroboration, [7] and hydrothiolation, [8] among others. Furthermore, methods for achieving 1,2-diheterofunctionalization of vinylferrocene through dibromination, [4] dihydroxylation, [9] and diazidation [10] have also been developed.…”

Section: Introductionmentioning

confidence: 99%

Catalyst‐Free Regioselective 1,2‐Diheterofunctionalization of Vinylferrocene

García‐Martínez,

Crespo,

González

et al. 2023

Eur J Inorg Chem

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In this study, we report a catalyst‐free aminohalogenation process applied to vinylferrocene, employing N‐halosuccinimides (NXS; X=Cl, Br, I) as dual nitrogen and halogen sources. This 1,2‐diheterofunctionalization reaction takes place with complete regioselectivity, wherein the terminal carbon atom of the vinyl group selectively reacts with the electrophilic halogenating reagent, resulting in the formation of a cationic intermediate, which is subsequently captured by the succinimide anion. The structure of the key cationic intermediate was studied using theoretical methods. This intermediate can react with alternative nucleophiles, enabling a three‐component strategy for the synthesis of novel 1,2‐diheterofunctionalized ferrocene derivatives.

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Section: Introductionmentioning

confidence: 99%

Catalyst‐Free Regioselective 1,2‐Diheterofunctionalization of Vinylferrocene

García‐Martínez,

Crespo,

González

et al. 2023

Eur J Inorg Chem

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“…Although several examples of PKR have been reported, practical implementations that lead to structurally dissimilar and thus separable products are not common in the literature. − In 2003, Tanaka and Fu reported a novel rhodium-catalyzed C–H activation of an alkyne-tethered aldehyde followed by regiodivergent cyclization with the alkyne to provide cyclobutanones and cyclopentenones in good yields and enantioselectivities but with limited substrate scope . Tanaka et al applied similar substrates and catalytic systems with isocyanate participating in intermolecular [4 + 2] cycloaddition as the competitive reaction pathway to intramolecular alkyne cycloaddition, leading to enantioselective derivatives of heptamide and cyclopentenone .…”

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confidence: 99%

Parallel Kinetic Resolution through Palladium-Catalyzed Enantioselective Cycloimidoylation: En Route to Divergent N-Heterocycles Bearing a Quaternary Stereogenic Center

Wang

Luo

et al. 2022

ACS Catal.

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An example of a parallel kinetic resolution catalyzed by palladium to produce enantioenriched five-and six-membered N-heterocycles in one pot was developed. Dihydroisoquinolines and 1H-isoindoles containing a quaternary stereogenic center were obtained from racemic isocyanides in high yields with good enantioselectivities under mild conditions. A 6,6′-dipropyl substituted SPINOL-derived phosphoramidite was used as the chiral ligand for the palladium catalyst, resulting in regiodivergent and stereospecific cycloimidoylation. Density functional theory (DFT) calculations reveal the origin of the regio-and enantioselectivity during the C(sp 2 )−H imidoylative cyclization process.

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Chemodivergent Parallel Kinetic Resolution of Paracyclophanes: Enantiomer Fishing with Different Substrates

Liu,

Teng,

Zhang

et al. 2024

Angewandte Chemie

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An unprecedented chemodivergent strategy for parallel kinetic resolution (PKR) is disclosed through which two planar chiral products bearing different structures were simultaneously afforded with opposite stereoselectivities. Two achiral esters are activated by one single chiral N‐heterocyclic carbene (NHC) catalyst to react with the different enantiomers of the racemic imine substrate in a parallel fashion. Two products bearing distinct structures and opposite stereoselectivities are respectively afforded from the same reaction system in good to excellent yields, enantio‐ and diastereoselectivities. Control experiments and kinetic studies are carried out to probe the kinetic and dynamic properties during the reaction progress. The planar chiral pyridine and lactam products show interesting applications in both asymmetric synthesis and pesticide development.

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Dynamic parallel kinetic resolution of α-ferrocenyl cation initiated by chiral Brønsted acid catalyst

Abstract: The dynamic parallel kinetic resolution (DPKR) of an α-ferrocenyl cation intermediate under the influence of a chiral conjugate base of a chiral phosphoric acid catalyst has been demonstrated in an...

Cited by 9 publications

References 57 publications

Catalyst‐Free Regioselective 1,2‐Diheterofunctionalization of Vinylferrocene

Catalyst‐Free Regioselective 1,2‐Diheterofunctionalization of Vinylferrocene

Parallel Kinetic Resolution through Palladium-Catalyzed Enantioselective Cycloimidoylation: En Route to Divergent N-Heterocycles Bearing a Quaternary Stereogenic Center

Chemodivergent Parallel Kinetic Resolution of Paracyclophanes: Enantiomer Fishing with Different Substrates

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