Studying the reactivity of alkyl substituted BODIPYs: first enantioselective addition of BODIPY to MBH carbonates

Meazza, Marta; Cruz, Carlos M.; Ortuño, A.; Cuerva, Juan M.; Crovetto, Luis; Rios, Ramón

doi:10.1039/d0sc06574a

“…In 2021, Rios and co‐workers developed an addition of BODIPYs to MBH carbonates, which showed nucleophilic character of carbon bonded to a meso position of BODIPY (Scheme 1). [12c] …”

Section: Figurementioning

confidence: 99%

Stereoselective Cyclopropanation of Boron Dipyrromethene (BODIPY) Derivatives by an Organocascade Reaction

Dočekal

¹

,

Koberová

²

,

Hrabovský

³

et al. 2021

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The synthesis of enantiopure chiral boron dipyrromethenes (BODIPYs) is of importance due the intrinsic properties of BODIPYs as fluorophores that could be used as probes for molecular sensing. The present study reports an asymmetric organocatalytic cascade reaction of meso‐chloromethyl BODIPY derivatives with α,β‐unsaturated aldehydes catalyzed by a chiral secondary amine. The corresponding BODIPY‐derived cyclopropanes were produced in isolated yields 66–98%, and with diastereomeric ratios 3/2–>20/1, and 92–99% ee for major diastereomer. The synthetic utility of the protocol was exemplified on a set of additional transformations of the corresponding optically pure compounds. In addition, a study explaining the reaction mechanism (DFT computations) and photophysical characterization of all enantioenriched products were accomplished.

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Catalytic Enantioselective Synthesis of Boron‐Stereogenic and Axially Chiral BODIPYs via Rhodium(II)‐Catalyzed C−H (Hetero) Arylation with Diazonaphthoquinones and Diazoindenines

Gao,

Liu,

Tian

et al. 2024

Angewandte Chemie

0

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The molecular engineering of boron dipyrromethenes (BODIPYs) has garnered widespread attention due to their structural diversity enabling tailored physicochemical properties for optimal applications. However, catalytic enantioselective synthesis of structurally diverse boron‐stereogenic BODIPYs through intermolecular desymmetrization and BODIPYs with atroposelectivity remains elusive. Here, we showcase rhodium(II)‐catalyzed site‐specific C‐H (hetero)arylations of prochiral BODIPYs and polysubstituted BODIPYs with diazonaphthoquinonesand diazoindenines, providing efficient pathways for the rapid assembly of versatile (hetero)arylated boron‐stereogenic and axially chiral BODIPYs through long‐range desymmetrization and axial rotational restriction modes. The synthetic application of the procedures has been emphasized by the efficient synthesis of BODIPY derivatives with various functions. Photophysical properties, bioimaging, and lipid droplet‐specific targeting capability of tailored BODIPYs are also demonstrated, indicating their promising applications in biomedical research, medicinal chemistry, and material science.

show abstract

Catalytic Enantioselective Synthesis of Boron‐Stereogenic and Axially Chiral BODIPYs via Rhodium(II)‐Catalyzed C−H (Hetero) Arylation with Diazonaphthoquinones and Diazoindenines

Gao,

Liu,

Tian

et al. 2024

Angew Chem Int Ed

0

View full text Add to dashboard Cite

The molecular engineering of boron dipyrromethenes (BODIPYs) has garnered widespread attention due to their structural diversity enabling tailored physicochemical properties for optimal applications. However, catalytic enantioselective synthesis of structurally diverse boron‐stereogenic BODIPYs through intermolecular desymmetrization and BODIPYs with atroposelectivity remains elusive. Here, we showcase rhodium(II)‐catalyzed site‐specific C‐H (hetero)arylations of prochiral BODIPYs and polysubstituted BODIPYs with diazonaphthoquinonesand diazoindenines, providing efficient pathways for the rapid assembly of versatile (hetero)arylated boron‐stereogenic and axially chiral BODIPYs through long‐range desymmetrization and axial rotational restriction modes. The synthetic application of the procedures has been emphasized by the efficient synthesis of BODIPY derivatives with various functions. Photophysical properties, bioimaging, and lipid droplet‐specific targeting capability of tailored BODIPYs are also demonstrated, indicating their promising applications in biomedical research, medicinal chemistry, and material science.

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Studying the reactivity of alkyl substituted BODIPYs: first enantioselective addition of BODIPY to MBH carbonates

Abstract: The first enantioselective addition of alkyl BODIPY to Morita-Baylis-Hillman (MBH) carbonates is reported. This is the first reported enantioselective methodology using the methylene position of BODIPYs as nucleophiles. The reaction...

Cited by 12 publications

References 66 publications

Stereoselective Cyclopropanation of Boron Dipyrromethene (BODIPY) Derivatives by an Organocascade Reaction

Stereoselective Cyclopropanation of Boron Dipyrromethene (BODIPY) Derivatives by an Organocascade Reaction

Catalytic Enantioselective Synthesis of Boron‐Stereogenic and Axially Chiral BODIPYs via Rhodium(II)‐Catalyzed C−H (Hetero) Arylation with Diazonaphthoquinones and Diazoindenines

Catalytic Enantioselective Synthesis of Boron‐Stereogenic and Axially Chiral BODIPYs via Rhodium(II)‐Catalyzed C−H (Hetero) Arylation with Diazonaphthoquinones and Diazoindenines

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