Memory of chirality in the phthalimide photocyclization of adamantane dipeptides

Ramljak, Tatjana Šumanovac; Sohora, Margareta; Antol, Ivana; Kontrec, Darko; Basarić, Nikola; Mlinarić‐Majerski, Kata

doi:10.1016/j.tetlet.2014.05.118

Cited by 22 publications

(10 citation statements)

References 38 publications

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“…Mlinarić-Majerski performed photolysis of chiral phthalimide 29, leading to enantiopure 11-membered lactam 32 (Scheme 9). 32 The absolute configuration of 32 was determined by its CD spectra, and the reaction was found to proceed with retention of configuration. Chiral biradical intermediate 30 was expected to be configurationally stabile due to the rigid and bulky structure of the adamantane moiety.…”

Section: Scheme 7 Double Moc In Recombination Of Two Radical Species:mentioning

confidence: 99%

Recent Progress in Memory Of Chirality (MOC): An Advanced Chiral Pool

Alezra

Kawabata

2016

Synthesis

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Section: Scheme 7 Double Moc In Recombination Of Two Radical Species:mentioning

confidence: 99%

Recent Progress in Memory Of Chirality (MOC): An Advanced Chiral Pool

Alezra

Kawabata

2016

Synthesis

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“…Substrate‐induced conformational control of a similar biradical macrocyclisation to form an 11‐membered ring product was previously observed by the authors in a separate study. In this instance, however, a single stereogenic centre in the precursor orchestrated the cyclisation with complete stereofidelity through a chiral memory effect [113] …”

Section: Photoinduced Electron Transfer In Peptide Macrocyclisationmentioning

confidence: 99%

“…Substrate-induced conformational controlo fasimilar biradical macrocyclisation to form an 11-membered ring product was previously observed by the authors in as eparate study.I nt his instance, however,as ingle stereogenic centre in the precursor orchestrated the cyclisation with complete stereofidelity throughachiral memory effect. [113] Mechanistically,t he macrocyclisation of C-terminal Phe substrates 60 a and 60 b was proposed to proceed in as imilar manner to that outlined in Figure 17 a. Direct PET from the carboxylate to the photoexcited-state phthalimide 62 is followed by decarboxylation (63 to 64), triplet to singlet ISC (intersystem crossing), cyclisation (64 to 65)a nd af inal amidol to amido ketone ring expansion (65 to 66;F igure 21).…”

Section: Intramolecular Pet-initiated Peptide Macrocyclisationmentioning

confidence: 99%

Photochemical Methods for Peptide Macrocyclisation

Raynal

Rose

Donald

et al. 2020

Chemistry A European J

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Photochemical reactions have been the subject of renewed interest over the last two decades, leading to the development of many new,d iversea nd powerful chemical transformations. More recently,t hese developments have been expanded to enable the photochemical macrocyclisation of peptidesa nd small proteins. These constructs benefit from increased stability, structuralr igidity and biological potency over their linear counterparts, providing opportunities for improved therapeutica gents. In this review,a no verview of both the established and emerging methods for photochemicalp eptide macrocyclisation is presented, highlighting both the limitations and opportunities for further innovation in the field.

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“…We found out that H-abstraction reactions were about ten times more efficient in the β-CD complexes than in the isotropic solution, and the macrocyclic host affected the stereochemistry of the reaction. Moreover, we studied photodecarboxylation reactions initiated by the phthalimide chromophore [17][18][19] and applied them in cyclizations with memory of chirality [20] and diastereoselective peptide cyclizations [21]. Photodecarboxylations were also intensively investigated in a series of nonsteroidal anti-inflammatory drugs [22][23][24] such as ketoprofen [25][26][27][28][29][30][31][32][33][34], due to photoallergic responses initiated by photodecarboxylation of these drugs [35].…”

Section: Introductionmentioning

confidence: 99%

[3 + 2] Cycloaddition with photogenerated azomethine ylides in β-cyclodextrin

Sohora

Mandić

Basarić

2020

Beilstein J. Org. Chem.

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Stability constants for the inclusion complexes of cyclohexylphthalimide 2 and adamantylphthalimide 3 with β-cyclodextrin (β-CD) were determined by 1H NMR titration, K = 190 ± 50 M−1, and K = 2600 ± 600 M−1, respectively. Photochemical reactivity of the inclusion complexes 2@β-CD and 3@β-CD was investigated, and we found out that β-CD does not affect the decarboxylation efficiency, while it affects the subsequent photochemical H-abstraction, resulting in different product distribution upon irradiation in the presence of β-CD. The formation of ternary complexes with acrylonitrile (AN) and 2@β-CD or 3@β-CD was also essayed by 1H NMR. Although the formation of such complexes was suggested, stability constants could not be determined. Irradiation of 2@β-CD in the presence of AN in aqueous solution where cycloadduct 7 was formed highly suggests that decarboxylation and [3 + 2] cycloaddition take place in the ternary complex, whereas such a reactivity from bulky adamantane 3 is less likely. This proof of principle that decarboxylation and cycloaddition can be performed in the β-CD cavity has a significant importance for the design of new supramolecular systems for the control of photoreactivity.

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Memory of chirality in the phthalimide photocyclization of adamantane dipeptides

Cited by 22 publications

References 38 publications

Recent Progress in Memory Of Chirality (MOC): An Advanced Chiral Pool

Recent Progress in Memory Of Chirality (MOC): An Advanced Chiral Pool

Photochemical Methods for Peptide Macrocyclisation

[3 + 2] Cycloaddition with photogenerated azomethine ylides in β-cyclodextrin

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