Recent Advancement in H<sub>8</sub>–BINOL Catalyzed Asymmetric Methodologies

Kshatriya, Rajpratap

doi:10.1021/acsomega.2c05535

Cited by 8 publications

(1 citation statement)

References 108 publications

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“…The enantiomers of 1,1′-bi-2-naphtol (BINOL) and related species play a key role in asymmetric organic synthesis and catalysis [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 ]. A recent noticeable example is constituted by the integration of chiral BINOL-phosphoric acid and Cu(II)-porphyrin modules into a single framework, able to promote the asymmetric α-benzylation of aldehydes via visible-light-induced photothermal conversion [ 14 ].…”

Section: Introductionmentioning

confidence: 99%

Luminescent Behavior of Zn(II) and Mn(II) Halide Derivatives of 4-Phenyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-Oxide and Single-Crystal X-ray Structure Determination of the Ligand

Ferraro,

Castro,

Bortoluzzi

2024

Molecules

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The two enantiomers of chiral phosphonate 4-phenyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide, O=PPh(BINOL), were synthesized from the proper 1,1′-bi-2-naphtol (BINOL) enantiomer and characterized. The structure of the (S)-enantiomer was elucidated by means of single-crystal X-ray diffraction. The reaction with anhydrous ZnBr2 afforded complexes having the general formula [ZnBr2{O=PPh(BINOL)}2] that showed intense fluorescence centered in the near-UV region rationalized on the basis of TD-DFT calculations. The corresponding Mn(II) complexes with the general formula [MnX2{O=PPh(BINOL)}2] (X = Cl, Br) exhibited dual emission upon excitation with UV light, with the relative intensity of the bands dependent upon the choice of the halide. The highest energy transition is comparable with that of the Zn(II) complex, while the lowest energy emission falls in the red region of the spectrum and is characterized by lifetimes in the hundreds of microseconds range. Although the emission at lower energy can also be achieved by direct excitation of the metal center, the luminescence decay curves suggest that the band in the red range is possibly derived from BINOL-centered excited states populated by intersystem crossing.

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Section: Introductionmentioning

confidence: 99%

Luminescent Behavior of Zn(II) and Mn(II) Halide Derivatives of 4-Phenyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-Oxide and Single-Crystal X-ray Structure Determination of the Ligand

Ferraro,

Castro,

Bortoluzzi

2024

Molecules

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Magnesium‐Catalyzed Asymmetric Thia‐Michael Addition to α,β‐Unsaturated Ketones

Jaszczewska‐Adamczak,

Baczewska,

Bujok

et al. 2024

Adv Synth Catal

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We demonstrate the application of chiral magnesium complexes in an asymmetric carbon‐sulfur bond‐forming reaction. Enantioselective and cost‐effective methodology under mild condition for the thia‐Michael addition, utilizing an in situ generated chiral dinuclear magnesium‐ProPhenol complex, has been developed. The versatility of this protocol is demonstrated with a broad range of thiol nucleophiles and a wide selection of enones. Enantioenriched β‐ketosulfides are obtained in good to excellent yields and moderate to excellent enantioselectivity. The presented catalytic system exhibits excellent tolerance for structurally different substrates while maintaining high enantioselectivity. This observation aligns with proposed mechanism, wherein the sulfur atom coordinates to the catalyst in close proximity to the reaction center.

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H₈‐BINOL‐Derived Chiral η⁶‐Benzene Ligands: New Opportunities for the Ruthenium‐Catalyzed Asymmetric C−H Activation

Li,

Wang,

Guo

et al. 2024

Angewandte Chemie

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Given the tremendous success of (p‐cymene)RuII‐catalyzed C−H activation over the past 20 years, the community has long been aware that the development of chiral η6‐benzene (Ben) ligands should be a potent strategy for achieving the attractive but incredibly underdeveloped ruthenium(II)‐catalyzed asymmetric C−H activation. However, it has rarely been achieved due to the severe difficulty in developing proper chiral Ben ligands. In particular, designing chiral Ben ligands by connecting a benzene fragment to a chiral framework including benzene rings remained an unsolved challenge until this effort. Here we present a novel class of axially chiral Ben ligands derived from readily available (S)‐5,5',6,6',7,7',8,8'‐octahydro‐1,1'‐bi‐2‐naphthol ((S)‐H8‐BINOL) in 4‐8 steps. Notably, when coordinated with ruthenium, such chiral Ben ligand containing three benzene rings only forms one of the three possible isomeric BenRuII complexes. The related chiral BenRuII catalysts could effectively catalyze the asymmetric C−H activation of N‐sulfonyl ketimines with alkynes, affording a range of chiral spirocyclic sultams in up to 99% yield with up to >99% ee. These catalysts are expected to find broad applications in future.

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Recent Advancement in H₈–BINOL Catalyzed Asymmetric Methodologies

Cited by 8 publications

References 108 publications

Luminescent Behavior of Zn(II) and Mn(II) Halide Derivatives of 4-Phenyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-Oxide and Single-Crystal X-ray Structure Determination of the Ligand

Luminescent Behavior of Zn(II) and Mn(II) Halide Derivatives of 4-Phenyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-Oxide and Single-Crystal X-ray Structure Determination of the Ligand

Magnesium‐Catalyzed Asymmetric Thia‐Michael Addition to α,β‐Unsaturated Ketones

H₈‐BINOL‐Derived Chiral η⁶‐Benzene Ligands: New Opportunities for the Ruthenium‐Catalyzed Asymmetric C−H Activation

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Recent Advancement in H8–BINOL Catalyzed Asymmetric Methodologies

Cited by 8 publications

References 108 publications

Luminescent Behavior of Zn(II) and Mn(II) Halide Derivatives of 4-Phenyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-Oxide and Single-Crystal X-ray Structure Determination of the Ligand

Luminescent Behavior of Zn(II) and Mn(II) Halide Derivatives of 4-Phenyldinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-Oxide and Single-Crystal X-ray Structure Determination of the Ligand

Magnesium‐Catalyzed Asymmetric Thia‐Michael Addition to α,β‐Unsaturated Ketones

H8‐BINOL‐Derived Chiral η6‐Benzene Ligands: New Opportunities for the Ruthenium‐Catalyzed Asymmetric C−H Activation

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Recent Advancement in H₈–BINOL Catalyzed Asymmetric Methodologies

H₈‐BINOL‐Derived Chiral η⁶‐Benzene Ligands: New Opportunities for the Ruthenium‐Catalyzed Asymmetric C−H Activation