Enantioselective fluorination of homoallylic alcohols enabled by the tuning of non-covalent interactions

Coelho, Jaime A. S.; Matsumoto, Akira; Orlandi, Manuel; Hilton, Margaret J.; Sigman, Matthew S.; Toste, F. Dean

doi:10.1039/c8sc02223b

Cited by 33 publications

(11 citation statements)

References 38 publications

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“…Recently, Sigman and co‐workers introduced computed interaction energies and distances as parameters for NCIs between aromatic rings and applied them successfully to several case studies . We wanted to test whether P int values could replace Sigman's energy parameters, which he termed Eπ, for the same type of multiple linear free‐energy relationship (MLFER) analysis.…”

Section: Resultsmentioning

confidence: 99%

“…However, it is not clear whether the increments are rather a measure of size as they correlated both with polarizabilities and surface areas. Additionally, Sigman and co‐workers proposed interaction parameters of substituted aromatic rings obtained from computed interaction energies, and successfully applied them to predict stereoselectivity in a number of catalytic reactions . Their main drawbacks are that they are quite expensive to compute, limited to aromatic systems, and account for more than just dispersion.…”

Section: Introductionmentioning

confidence: 99%

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A Universal Quantitative Descriptor of the Dispersion Interaction Potential

Pollice

Chen

2019

Angewandte Chemie

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London dispersion, universally attractive forces originating from fluctuating dipoles,i so mnipresent in molecules.W hile its understanding has recently made tremendous progress,i ts general appreciation is still lagging behind electrostatics.T his can be explained by the simple tools available to study electrostatic interactions,such as electrostatic potential (ESP) maps and partial charges,a nd al ackt hereof for dispersion. We herein report au niversal quantitative descriptor of dispersion interaction potentials,w hicha llows assessing dispersion visually by London dispersion potential (LDP) maps,and quantitatively using the average LDP on the van der Waals surface.W edemonstrate the utility of these new tools by constructing aq uantitative dispersion energy scale of the elements and common substituents,s tudying non-covalent interactions (NCIs), and developing modern linear free energy relationships in catalysis.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Universal Quantitative Descriptor of the Dispersion Interaction Potential

Pollice

Chen

2019

Angewandte Chemie

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“…One equivalent of 4-fluorophenylboronic acid was added to generate a boronate ester directing group in situ (see refs. [113][114][115] for similar in situ directing group formations). 4 Å molecular sieves and five equivalents of H 2 O were added to fine-tune boronate ester formation.…”

Section: Fluorinative Dearomatization Reactionsmentioning

confidence: 86%

“…Later, the above method was extended to homoallylic alcohols. The products were obtained with good to excellent ee values but in moderate yields [115] . Allylic 2‐hydroxyphenyl substituents were also appropriate directing groups for enantioselective phase‐transfer fluorination of alkenes [116] …”

Section: Asymmetric C−f Bond‐forming Reactions Using Chiral Phase‐transfer Catalysismentioning

confidence: 99%

“…The products were obtained with good to excellent ee values but in moderate yields. [115] Allylic 2-hydroxyphenyl substituents were also appropriate directing groups for enantioselective phase-transfer fluorination of alkenes. [116] Toste and coworkers reported that compounds with an Nacyl-3-phenylbut-2-en-1-amine moiety also underwent asymmetric deprotonative fluorination.…”

Section: Fluorinative Transformations Of Alkenesmentioning

confidence: 99%

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Asymmetric Methods for Carbon‐Fluorine Bond Formation

et al. 2021

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In memory of Ferenc FülöpAs a consequence of the ever-increasing relevance of fluorinated drugs in medicinal chemistry, organofluorine chemistry has become a hot topic research area during the last decade. Asymmetric carbon-fluorine bond-forming reactions have enormously developed in recent years with considerable findings related to novel reactions and synthetic approaches. These new synthetic efforts have contributed to the access to a growing number of fluorinated molecules and complex natural or synthetic products of high relevance in medicinal chemistry and drug research. Illustrative examples of novel synthetic methodologies, including organocatalytic processes, asymmetric syntheses or phase-transfer catalytic methods for the enantioselective incorporation of fluorine atom(s) into versatile molecular entities, are covered in the current Review, focusing on main contributions of the last ten years.

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Catalytic, Enantioselective Fluorination Reactions

Thornbury

Toste

2019

Organic Reactions

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The unique properties conferred by the incorporation of fluorine into organic molecules has resulted in the widespread use of organofluorine compounds in the pharmaceutical and agrochemical industries. In contrast, organofluorine compounds are exceedingly rare in nature. The dearth of chiral pool organofluorine compounds necessitates the development of stereoselective methods for the incorporation of carbon–fluorine bonds into organic molecules. A wide variety of catalytic, enantioselective fluorination methods have been developed to address this challenge, including Lewis acid catalysis, organocatalysis, transition metal catalysis, and phase transfer catalysis. Using these methods, carbonyl compounds, alkenes, allylic electrophiles, aziridines, and epoxides have been engaged in catalytic, enantioselective fluorination reactions. This chapter provides a comprehensive review of the methods available for the catalytic, enantioselective construction of carbon–fluorine bonds and is subdivided into electrophilic and nucleophilic fluorination reactions. The chapter also provides a comparison with diastereoselective transformations and enantioselective functionalization reactions of fluorinated substrates.

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Enantioselective fluorination of homoallylic alcohols enabled by the tuning of non-covalent interactions

Abstract: Multivariate correlation analysis, including designer π-interaction derived parameters, was applied to the study of the enantioselective fluorination of homoallylic alcohols via chiral anion phase transfer (CAPT) catalysis.

Cited by 33 publications

References 38 publications

A Universal Quantitative Descriptor of the Dispersion Interaction Potential

A Universal Quantitative Descriptor of the Dispersion Interaction Potential

Asymmetric Methods for Carbon‐Fluorine Bond Formation

Catalytic, Enantioselective Fluorination Reactions

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