BODIPY as electron withdrawing group for the activation of double bonds in asymmetric cycloaddition reactions

Guerrero-Corella, Andrea; Asenjo‐Pascual, Juan; Pawar, Tushar Janardan; Díaz‐Tendero, Sergio; Martín-Sómer, Ana; Gómez, Clarisa Villegas; Belmonte‐Vázquez, José L.; Ramírez‐Ornelas, Diana E.; Peña‐Cabrera, Eduardo; Fraile, Alberto; Cruz, David Cruz; Alemán, José V.

doi:10.1039/c9sc00959k

Cited by 21 publications

(7 citation statements)

References 61 publications

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“…In 2019, Aleman and co‐workers reported the first enantioselective methodology for the synthesis of chiral BODIPYs, taking advantage of their EWG properties for the activation of a conjugated double bond [12a,b] . 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).…”

Section: Figurementioning

confidence: 99%

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

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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Section: Figurementioning

confidence: 99%

“…[11] In sharp contrast to the potential of chiral BODIPYs, enantioselective catalytic approaches for their preparation remained virtually unexplored. [12] For this reason, we have become interested in developing new enantioselective methodologies allowing the construction of enantiopure BODIPYs.…”

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confidence: 99%

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

et al. 2021

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“…In this sense, 2,4‐dienals 8 , were treated with alkenyl‐BODIPY derivatives 94 in presence of Cat. 17 , to furnish the cycloahexane derivatives containing the BODIPY unit, which after the treatment with the corresponding triphenylphosphorane leads to 95 in good to excellent yields and high to excellent enantioselectivities (Scheme ) …”

Section: Dienals and Dienones In Trienamine Catalysismentioning

confidence: 99%

Polyenals and Polyenones in Aminocatalysis: A Decade Building Complex Frameworks from Simple Blocks

et al. 2020

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Polyenals and polyenones are simple chemical compounds which can be constructed into large and complex structures by virtue of aminocatalysis. In the past eight years, new aminocatalytic activation modes based on trienamine, cross-trienamine, tetraenamine, iminium ion, and vinylogous iminium ion intermediates have attracted great attention in the field of asymmetric synthesis. Key to the increasing focus is their inherent ability to allow functionalization of remote sites with excel-[a] Dr.

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“…This was mainly because DF, the dienophile with an electron-withdrawing group, was more favorable for the Diels-Alder reaction than FA [33]. According to frontier molecular orbital theory (FMO), the Diels-Alder reaction is controlled by the suprafacial in-phase interaction of the highest occupied molecular orbital (HOMO) of one component and the lowest unoccupied molecular orbital (LUMO) of the other [34,35].…”

Section: The Role Of Iodine In Diels-alder Reactionmentioning

confidence: 99%

The Role of Iodine Catalyst in the Synthesis of 22-Carbon Tricarboxylic Acid and Its Ester: A Case Study

et al. 2019

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Here, 22-carbon tricarboxylic acid (C22TA) and its ester (C22TAE) were prepared via the Diels–Alder reaction of polyunsaturated fatty acids (PUFAs) and their esters (PUFAEs) as dienes with fumaric acid (FA) and dimethyl fumarate (DF) as dienophiles, respectively. The role of an iodine catalyst for the synthesis of C22TA and C22TAE in the Diels–Alder type reaction was investigated using a spectroscopic approach. The chemical structures of the products were characterized using proton nuclear magnetic resonance (1H-NMR) and electrospray ionization mass spectrometry (ESI-MS) analysis. Results showed that nonconjugated dienes can react with dienophiles through a Diels–Alder reaction with an iodine catalyst, and that iodine transformed the nonconjugated double bonds of dienes into conjugated double bonds via a radical process. DF was more favorable for the Diels–Alder reaction than FA. This was mainly because the dienophile DF contained an electron-withdrawing substituent, which reduced the highest and lowest occupied molecular orbital (HOMO–LUMO) energy gap and accelerated the Diels–Alder reaction. By transforming nonconjugated double bonds into conjugated double bonds, iodine as a Lewis acid increased the electron-withdrawing effect of the carbonyl group on the carbon–carbon double bond and reduced the energy difference between the HOMO of diene and the LUMO of dienophile, thus facilitating the Diels–Alder reaction.

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BODIPY as electron withdrawing group for the activation of double bonds in asymmetric cycloaddition reactions

Abstract: BODIPY as an EWG in asymmetric catalysis is presented.

Cited by 21 publications

References 61 publications

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

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

Polyenals and Polyenones in Aminocatalysis: A Decade Building Complex Frameworks from Simple Blocks

The Role of Iodine Catalyst in the Synthesis of 22-Carbon Tricarboxylic Acid and Its Ester: A Case Study

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