Fluorocyclopropane-Containing Proline Analogue: Synthesis and Conformation of an Item in the Peptide Chemistʼs Toolbox

Pons, Amandine; Decaens, Jonathan; Najjar, Riham; Otog, Nansalmaa; Arribat, Mathieu; Jolly, Sandrine; Couve‐Bonnaire, Samuel; Sebban, Muriel; Coadou, Gaël; Oulyadi, Hassan; Speybrouck, David; Iwasa, Seiji; Charette, André B.; Poisson, Thomas; Jubault, Philippe

doi:10.1021/acsomega.1c05337

Cited by 4 publications

(2 citation statements)

References 41 publications

(43 reference statements)

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“…We will the most probably see soon the synthesis of unknown fluoromethyl- and difluoromethyl-substituted prolines, as well as some of fluorinated bicyclic prolines. We are also about to see novel intriguing applications of fluorinated prolines, for example, in organocatalysis, given its recent recognition at the highest scientific level. , …”

Section: Discussionmentioning

confidence: 99%

Fluorine-Containing Prolines: Synthetic Strategies, Applications, and Opportunities

Mykhailiuk

2022

J. Org. Chem.

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Fluorinated prolines play an important role in peptide studies, protein engineering, medicinal chemistry, drug discovery, and agrochemistry. Since the first synthesis of 4-fluoroprolines by Gottlieb and Witkop in 1965, their popularity started to grow exponentially. For example, during the past two decades, all isomeric trifluoromethyl-substituted prolines have been synthesized. In this Perspective, chemical properties and applications of fluorinated prolines are discussed. Synthetic approaches to all known fluorine-containing prolines are also discussed and analyzed. This analysis unexpectedly revealed an unsolved problem: in strict contrast to fluoro- and trifluoromethyl-substituted prolines, the corresponding analogues with fluoromethyl and difluoromethyl groups are mostly unknown. At the end of the paper, structures of several interesting, yet unknown, fluorinated prolines are discloseda good opportunity for chemists to make them.

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Section: Discussionmentioning

confidence: 99%

Fluorine-Containing Prolines: Synthetic Strategies, Applications, and Opportunities

Mykhailiuk

2022

J. Org. Chem.

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“…Occasionally, the same conversion starting from enyne analogues has also been achieved by a photocatalytic pathway [34][35][36] as well as metal-free organocatalytic processes [37][38][39][40][41][42], mechanisms that are similar to the metal carbene processes (Scheme 1a). Another two effective approaches for the synthesis of 3-azabicyclo[3.1.0]hexanes involve the derivatization reactions of substituted cyclopropanes, such as C(sp 3 )-H bond activated alkenylation/amination tandem reactions and intramolecular aminolysis reactions Molecules 2023, 28, 3691 2 of 15 (Scheme 1b) [43][44][45][46][47][48][49][50][51][52][53], and the reaction of functionalized maleimide derivatives with one carbon donor generated in situ derived from substituted diazomethanes, bromo(nitro)methane, substituted α-diazoacetates, and N-tosylhydrazones via an intermolecular [2+1] fusedannulation reaction (Scheme 1c) [54][55][56][57][58][59][60][61][62][63][64]. In particular, the base-induced intramolecular spirocyclization method of the alkylation subunit precursor appeared to be a more efficient proprietary reaction to access 3-azabicyclo[3.1.0]hexane scaffold-containing natural products via aryl metal or radical dearomatization/cyclization reactions (Scheme 1d) [65][66][67][68][69][70][71]…”

Section: Introductionmentioning

confidence: 99%

Base-Promoted Intramolecular Addition of Vinyl Cyclopropanecarboxamides to Access Conformationally Restricted Aza[3.1.0]bicycles

Zhang

Chen

et al. 2023

Molecules

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3-Azabicyclo[3.1.0]hexanes are common structural components in natural products and bioactive compounds. Traditionally, the metal-mediated cyclopropanation domino reaction of chain enzymes is the most commonly used strategy for the construction of this type of aza[3.1.0]bicycle derivative. In this study, a base-promoted intramolecular addition of alkenes used to deliver conformationally restricted highly substituted aza[3.1.0]bicycles is reported. This reaction was tailor-made for saturated aza[3.1.0] bicycle-containing fused bicyclic compounds that may be applied in the development of concise and divergent total syntheses of bioactive compounds.

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Catalytic Asymmetric Syntheses of Alkylidenecyclopropanes from Allenoates with Donor‐Acceptor and Diacceptor Diazo Reagents

Hasegawa

Cantin

Decaens

et al. 2022

Chemistry A European J

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The first diastereo-and enantioselective cyclopropanation reactions of electron-deficient allenes with donor-acceptor and diacceptor diazo reagents are described. The desired enantioenriched alkylidenecyclopropanes (ACPs) were obtained in high yields with high diastereo-and enantioselectivities in the presence of Rh 2 ((S)-TCPTAD) 4 or Rh 2 ((R)-BTPCP) 4 catalysts (up to 95 % yield, > 95 : 5 d.r. and 99 : 1 e.r.). This methodology gave a direct access to ACPs bearing multiple electron-deficient substituents and allows to further expand the availability of ACPs chemistry. Interestingly, during the examination of the scope of this reaction, the asymmetric intramolecular CÀ H insertion reaction into tert-butyl group was observed as a side reaction with up to 94 : 6 e.r.

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Fluorocyclopropane-Containing Proline Analogue: Synthesis and Conformation of an Item in the Peptide Chemistʼs Toolbox

Cited by 4 publications

References 41 publications

Fluorine-Containing Prolines: Synthetic Strategies, Applications, and Opportunities

Fluorine-Containing Prolines: Synthetic Strategies, Applications, and Opportunities

Base-Promoted Intramolecular Addition of Vinyl Cyclopropanecarboxamides to Access Conformationally Restricted Aza[3.1.0]bicycles

Catalytic Asymmetric Syntheses of Alkylidenecyclopropanes from Allenoates with Donor‐Acceptor and Diacceptor Diazo Reagents

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