Kinetic Resolution of β-Hydroxy Carbonyl Compounds via Enantioselective Dehydration Using a Cation-Binding Catalyst: Facile Access to Enantiopure Chiral Aldols

Paladhi, Sushovan; Hwang, In Soo; Yoo, Eun Jeong; Ryu, Do Hyun; Song, Choong Eui

doi:10.1021/acs.orglett.8b00547

Cited by 17 publications

(13 citation statements)

References 37 publications

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“… 30 Soon after, chiral BINOL-derived polyether catalysts (e.g., 13 , Scheme 4 B) proved to be highly selective in the desilylative kinetic resolution of silylated alcohols 7 . 31 By employing KF as a base rather than a nucleophile, asymmetric β-eliminations of β-sulfonyl ketones 10 ( Scheme 4 B), 32 anti - syn -trihalides, and anti - syn - anti -tetrahalides were disclosed. 33 This strategy was also applied to Strecker 5d and silylation reactions, 34 yet no examples involving C–F bond formation reactions ensued.…”

Section: The Fluorinase Enzyme and Hydrogen-bonded Fluoride Complexesmentioning

confidence: 99%

Hydrogen Bonding Phase-Transfer Catalysis with Alkali Metal Fluorides and Beyond

Pupo

Gouverneur

2022

J. Am. Chem. Soc.

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Phase-transfer catalysis (PTC) is one of the most powerful catalytic manifolds for asymmetric synthesis. Chiral cationic or anionic PTC strategies have enabled a variety of transformations, yet studies on the use of insoluble inorganic salts as nucleophiles for the synthesis of enantioenriched molecules have remained elusive. A long-standing challenge is the development of methods for asymmetric carbon–fluorine bond formation from readily available and cost-effective alkali metal fluorides. In this Perspective, we describe how H-bond donors can provide a solution through fluoride binding. We use examples, primarily from our own research, to discuss how hydrogen bonding interactions impact fluoride reactivity and the role of H-bond donors as phase-transfer catalysts to bring solid-phase alkali metal fluorides in solution. These studies led to hydrogen bonding phase-transfer catalysis (HB-PTC), a new concept in PTC, originally crafted for alkali metal fluorides but offering opportunities beyond enantioselective fluorination. Looking ahead, the unlimited options that one can consider to diversify the H-bond donor, the inorganic salt, and the electrophile, herald a new era in phase-transfer catalysis. Whether abundant inorganic salts of lattice energy significantly higher than those studied to date could be considered as nucleophiles, e.g., CaF 2 , remains an open question, with solutions that may be found through synergistic PTC catalysis or beyond PTC.

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Section: The Fluorinase Enzyme and Hydrogen-bonded Fluoride Complexesmentioning

confidence: 99%

Hydrogen Bonding Phase-Transfer Catalysis with Alkali Metal Fluorides and Beyond

Pupo

Gouverneur

2022

J. Am. Chem. Soc.

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“…Recently, we reported an easily accessible BINOL-based bis(hydroxy) polyethers bearing phenols and polyether units for asymmetric cation-binding catalysis . The ether oxygens act as a Lewis base to coordinate metal ions such as K + , thus generating a soluble chiral anion, which can be used as the base or nucleophile in a confined chiral space.…”

Section: Introductionmentioning

confidence: 99%

Kinetic Resolution of Allylic Alcohol with Chiral BINOL-Based Alkoxides: A Combination of Experimental and Theoretical Studies

Liu¹,

Liu²,

Li³

et al. 2018

J. Am. Chem. Soc.

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The development and characterization of enantioselective catalytic kinetic resolution of allylic alcohols through asymmetric isomerization with chiral BINOL derivatives-based alkoxides as bifunctional Brønsted base catalysts were described in the study. A number of chiral BINOL derivatives-based alkoxides were synthesized, and their structure−enantioselectivity correlation study in asymmetric isomerization identified a promising chiral Brønsted base catalyst, which afforded various chiral secondary allylic alcohols (ee up to 99%, S factor up to >200). In the mechanistic study, alkoxide species were identified as active species and the phenol group of BINOL largely affected the high reactivity and enantioselectivity via hydrogen bonding between the chiral Brønsted base catalyst and substrates. The strategy is the first successful synthesis strategy of various chiral secondary allylic alcohols through enantioselective transitionmetal-free base-catalyzed isomerization. The applicability of the strategy had been demonstrated by the synthesis of the bioactive natural product (+)-veraguensin.

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“…Less than a decade ago, we developed easily accessible and efficient multifunctional 1,1′-bi-2-naphthol (BINOL)-based organocatalysts (Song’s oligoEGs 1 , Scheme , eq 3) , bearing polyether-tethered free phenol groups for asymmetric cation-binding catalysis. Metal ions such as K + coordinate with the Lewis basic ether oxygen sites to generate a soluble chiral anion in a confined chiral space.…”

mentioning

confidence: 99%

“…Moreover, terminal phenol groups are capable of simultaneously activating the electrophile by hydrogen bonding interaction, resulting in a well-organized transition state. Several challenging catalytic asymmetric reactions have been successfully accomplished using Song’s chiral oligoEGs as an evolved cation-binding catalytic system based on the above-described ambiphilic activation mechanism . The ease of modulation and vast application potential of this systematic cooperative hydrogen-bonding catalytic system led us to explore challenging intramolecular cycloetherification reactions using Song’s oligoEGs for the synthesis of enantioenriched 2-substituted oxacycles.…”

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confidence: 99%

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Organocatalytic Enantioselective Cycloetherifications Using a Cooperative Cation-Binding Catalyst

Jadhav

Hwang

et al. 2018

Org. Lett.

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A highly enantioselective cycloetherification strategy for the straightforward synthesis of enantioenriched tetrahydrofurans, tetrahydropyrans, and oxepanes using Song's cation-binding oligoEG catalyst and KF as the base is demonstrated. A wide range of ε-, ζ-, and η-hydroxy-α,β-unsaturated ketones were cyclized to the corresponding five-, six-, and seven-membered chiral oxacycles with high enantiopurity. This remarkably successful catalysis can be ascribed to systematic cooperative cation-binding catalysis in a densely confined supramolecular chiral cage generated in situ from the chiral catalyst, substrate, and KF.

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Kinetic Resolution of β-Hydroxy Carbonyl Compounds via Enantioselective Dehydration Using a Cation-Binding Catalyst: Facile Access to Enantiopure Chiral Aldols

Cited by 17 publications

References 37 publications

Hydrogen Bonding Phase-Transfer Catalysis with Alkali Metal Fluorides and Beyond

Hydrogen Bonding Phase-Transfer Catalysis with Alkali Metal Fluorides and Beyond

Kinetic Resolution of Allylic Alcohol with Chiral BINOL-Based Alkoxides: A Combination of Experimental and Theoretical Studies

Organocatalytic Enantioselective Cycloetherifications Using a Cooperative Cation-Binding Catalyst

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