Enantioselective Radical Type, 1,2-Oxytrifluoromethylation of Olefins Catalyzed by Chiral Vanadyl Complexes: Importance of Noncovalent Interactions

Chen, Chien Tien; Su, Yu-Cheng; Lu, Chia Hao; Lien, Chien; Hung, Shiang Fu; Hsu, Chan Wei; Agarwal, Rachit; Modala, Ramuasagar; Tseng, Hung Min; Tseng, Pin Xuan; Fujii, Ryoma; Kawashima, Kyohei; Mori, Susumu

doi:10.1021/acscatal.1c01813

Cited by 14 publications

(12 citation statements)

References 63 publications

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“…In the past 15 years, we have developed several salicylidene L-t-leucinate ligands as ion-channel protein memetics for filtering monovalent K + and Ag(CH 3 CN) + as well as divalent Ba 2+ and Hg(NO 3 ) + -specific encapsulation and transport (Figure 1). 12,13 In particular, the strength of the K + ion complexation (K a ≈ 10 10 M −1 ) by a square planar motif was estimated to be at least 100 times stronger than that exerted by dicylohexano-18-crown-6. Inspired by these successful advances and catalysis applications, 14,15 we sought to append a 4-heptoxyphenyl group at the C5 position of the salicylidene template to impart a nematic LC functional unit directly into the vanadyl monomer (Figure 2A).…”

Section: ■ Introduction and Backgroundmentioning

confidence: 99%

“…It has been known that there remained one nitrate ligand sitting on top of Hg 2+ in a capped prism complexation mode for a 3,5dibromo-substituted cluster reported previously by us. 13 One would expect 3′-Hg(NO 3 ) to hold a similar complexation geometry.…”

Section: ■ Introduction and Backgroundmentioning

confidence: 99%

“…Figure1. Previous studies on metal ion-specific encapsulation and swapping in our group 12,13. Reproduced with permission from refs 12 and 13.…”

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confidence: 99%

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Metal-Ion Specific Recognition with Amplified Transcription from Subnanometer to Submillimeter or Real-Time Domain by Self-Assembled Vanadyl Quartets

Chen

Weng

2022

Inorg. Chem.

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Vanadyl(V) complexes 1 and 2 bearing a nematic liquid crystal (LC) like a p-heptoxyphenyl group or a fluorous-tag pnonafluoroheptoxyphenyl (NFH) group at the C5 position of the Nsalicylidene template were designed and synthesized. Each complex was subjected to MVO 3 -induced self-assembly to form metal-ion, encapsulated quartet clusters 3-M and 3′-M. The Na + in cluster complex 3-Na or 3′-Na can be readily replaced by Rb + , Ag + , or Hg 2+ in an aqueous layer to form cluster complexes by ion swapping at the H 2 O/CDCl 3 bilayer interface. Selectivity profiles were examined with alkali-metal ions, Ag + , and Hg 2+ through metal-ion competition experiments. The 3′-Na has an exclusive selectivity for Hg 2+ in the presence of Zn 2+ and Cd 2+ . Cluster complexes 3-M were utilized as chiral dopants to nematic LC materials. The effects of the encapsulated metal ions within the alkali family and Ag + on Cano's line widths and helical pitch changes were viewed in wedge cells under a polarized microscope. Their correlations with the ionic radius were identified. The subnano information of the metal ions can thus be asymmetrically amplified to Cano's line spacings of the submilimeter domain. Conversely, the effects of the encapsulated alkali metal ions and Hg 2+ in 3′-M on the interactions of their NFH tails toward fluorous silica gel (FSG) were performed via HPLC analyses. Their retention times became longer as the sizes of encapsulated, alkali metal ions increased. The increasing ion size from Na + to Cs + caused the four lower rim NFH tags of the cluster to be closer due to reduced cone angles. Their interactions among NFH tail groups on FSG became larger, thus leading to distinctive separations with t R from 7.36 to 10.27 min. The retention time difference between 3′-Na and 3′-Hg on HPLC was ∼3.6 min, resulting in discernible separation. The individual ion size differences on the subnano scale can thus be amplified and unambiguously established in the real time domain.

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Section: ■ Introduction and Backgroundmentioning

confidence: 99%

Section: ■ Introduction and Backgroundmentioning

confidence: 99%

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Metal-Ion Specific Recognition with Amplified Transcription from Subnanometer to Submillimeter or Real-Time Domain by Self-Assembled Vanadyl Quartets

Chen

Weng

2022

Inorg. Chem.

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“…complexes have been explored for the synthesis of block copolymers through bridging ROCOP and ROP reactions, ,,,− among which salen-Cr complexes exhibit wide monomer scope, good activity, high selectivity, and reliable molecular weight controllability. − Hence, Cr complexes were chosen as ideal candidates. Noncovalent interactions played a remarkable role in the catalytic activity and monomer recognition, − among which the N–H bond of rigid o -aminophenolate moieties in catam ligands endowed metal complexes with a high catalytic activity for cyclic ester polymerization. − Therefore, we designed a novel Cr complex 1 chelated with an asymmetric ligand (containing one salen bond and one catam bond, Scheme b) for the preparation of gradient terpolymers from cyclohexene oxide (CHO), CO 2 , and ε-caprolactone (ε-CL). The reaction process and the relationship of chain configurations with reaction conditions were investigated in detail.…”

Section: Introductionmentioning

confidence: 99%

Facile Synthesis of Gradient Polycarbonate–Polyester Terpolymers from Monomer Mixtures Mediated by an Asymmetric Chromium Complex

Zhou

Gao

et al. 2022

Macromolecules

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Gradient polycarbonate–polyester copolymers possess distinctive biodegradable and physicochemical properties in comparison with block or random copolymers. However, their synthesis is still a challenge due to the distinct chain-growth mechanisms among various monomers. Herein, we designed a novel asymmetric Cr complex containing a N–H bond of rigid o-aminophenolate moieties. Compared with the typically analogous symmetric salen-Cr(Cl) complex, the well-designed ligand endowed the asymmetric Cr complex with an exceptional ability to synthesize gradient biodegradable terpolymers from monomer mixtures of cyclohexene oxide, CO2, and ε-caprolactone. Specifically, gradient terpolymers were validated by investigating reaction processes and chain microstructures. It should be noted that the configurations of gradient terpolymers could be modulated by adjusting reaction conditions and component ratios, which further influenced the physicochemical properties. The synthetic approach in this work could open avenues to a wide variety of novel gradient copolymers and modify the property of biodegradable materials.

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“…NCIs, such as hydrogen bonding and dispersion interactions, can be revealed by a method introduced by Johnson et al . NCI is a prevalent interaction for asymmetric synthesis, and we have determined the origin of enantioselection for various asymmetric organic reactions and the reactivity for enzymatic reactions using NCI analysis. The results of the NCI analyses are shown in Figure .…”

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confidence: 99%

Integrated Experimental and Computational Studies on the Organocatalytic Kinetic Resolution of β-Unfunctionalized Primary Alcohols Using a Chiral 1,2-Diamine: The Importance of Noncovalent Interactions

et al. 2022

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The enantioselective kinetic resolution of β-unfunctionalized primary alcohols with benzoyl chloride was carried out in the presence of a catalytic amount of a novel chiral 1,2-diamine derived from (S)-proline. Several valuable chiral 2-substituted propan-1-ols were obtained with good enantioselectivities. Density functional theory calculations revealed that the noncovalent interaction, such as CH−π interaction, is crucial for the enantioselectivity of the resolution. This study was conducted through an interplay between experiment and computation.C hiral 2-phenyl-1-propanol is a promising synthon because this skeleton has applications in anti-inflammatory drugs such as naproxol, ibuprofen, and others. Its derivatives are also used as precursors for the total synthesis of natural products. 1 Chiral 2-phenyl-1-propanol can be obtained by various methods 2−6 (Scheme 1). In 2017, Rychnovsky et al. reported the kinetic resolution of 2-phenyl-1-propanol using homobenzotetramisole (HBTM) and resolution proceeded with a selectivity (s) of ≤6.2 (Scheme 1e). 6 The kinetic resolution of racemic alcohols has been widely utilized to construct valuable chiral building blocks for the synthesis of pharmaceuticals and natural compounds. 7 In particular, the enzymatic kinetic resolution of racemic alcohols has been used as one of the most effective methods 8 for the synthesis of optically active alcohols. In recent decades, the asymmetric acylation of alcohols using organocatalysts has emerged as a powerful approach, and the kinetic resolution of racemic secondary alcohols has been reported many times. 9 However, the kinetic resolution of racemic primary alcohols is limited to a few examples. 10 In 2005, our group reported the first non-enzymatic kinetic resolution of primary alcohols using chiral 1,2-diamine organocatalysts. 11 Chiral 1,2-diamines derived from (S)-proline are excellent organocatalysts for the catalytic asymmetric synthesis of many valuable organic compounds. Pioneering studies by T. Mukaiyama established various asymmetric syntheses using chiral 1,2-diamines readily derived from (S)-proline, including reduction of acetophenone, 12 Grignard reaction to alde-

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Enantioselective Radical Type, 1,2-Oxytrifluoromethylation of Olefins Catalyzed by Chiral Vanadyl Complexes: Importance of Noncovalent Interactions

Cited by 14 publications

References 63 publications

Metal-Ion Specific Recognition with Amplified Transcription from Subnanometer to Submillimeter or Real-Time Domain by Self-Assembled Vanadyl Quartets

Metal-Ion Specific Recognition with Amplified Transcription from Subnanometer to Submillimeter or Real-Time Domain by Self-Assembled Vanadyl Quartets

Facile Synthesis of Gradient Polycarbonate–Polyester Terpolymers from Monomer Mixtures Mediated by an Asymmetric Chromium Complex

Integrated Experimental and Computational Studies on the Organocatalytic Kinetic Resolution of β-Unfunctionalized Primary Alcohols Using a Chiral 1,2-Diamine: The Importance of Noncovalent Interactions

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