Photoinduced hydrogen atom abstraction in N-(adamantyl)phthalimides: structure–reactivity study in the solid state

Basarić, Nikola; Horvat, Margareta; Franković, Oliver; Mlinarić‐Majerski, Kata; Neudörfl, Jörg‐M.; Griesbeck, Axel G.

doi:10.1016/j.tet.2008.12.010

Cited by 21 publications

(25 citation statements)

References 34 publications

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“…The NMR spectroscopic data of products 21 and 22 are in accord with those in the literature [72]. The NMR spectroscopic data of products 21 and 22 are in accord with those in the literature [72].…”

supporting

confidence: 86%

“…On the basis of literature precedent, [46,72] the excitation of phthalimides 3-6 in the presence of a base to deprotonate the carboxylic group is anticipated to lead to an irreversible PET decarboxylation and deliver simple decarboxylation or cyclization products. To probe the reactivity of phthalimides 3-6 towards decarboxylation, these compounds were irradiated at 300 nm in the presence of 0.5 equiv.…”

Section: Photochemical Reactivitymentioning

confidence: 99%

“…ence of 0.5 equiv. Because 23 could undergo a photochemical intramolecular H-abstraction to give 24 and 25, [73,74] it was important to investigate whether 24 was formed from the decarboxylative cyclization of 5 or from 23 (Scheme 7). Phthalimide 3 was irradiated until a high conversion was reached to cleanly afford phthalimide 21 (Scheme 5).…”

Section: Photochemical Reactivitymentioning

confidence: 99%

“…The reaction mixture was cooled to 0°C by using an ice bath, and tBuOK (350 mg, 3.12 mmol) was added in two portions over 10 min. [72] Quantum Yield of Photodecarboxylation: The quantum yield of photodecomposition was determined by using a secondary actinometer, that is, the photolysis of 31 in CH 3 CN/H 2 O (3:1) to give 32 and 33 (Φ R = 0.30 ± 0.03). The stirring was continued overnight, as the mixture was heated to 45°C.…”

Section: Methyl 2-cyanoadamantane-1-carbamate (13me)mentioning

confidence: 99%

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Photodecarboxylation of Adamantane Amino Acids Activated by Phthalimide

et al. 2016

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Adamantane α‐, β‐, and δ‐amino acids activated by phthalimide (i.e., 3–6) were synthesized, and their photochemical reactivities were investigated. Amino acid derivatives 3–6 underwent a photoinduced electron transfer (PET) and decarboxylation reaction sequence, most probably through a triplet excited state. The decarboxylations of the β‐amino acid derivatives were succeeded by cyclization reactions that afforded complex polycyclic molecules with potential biological interest. The adamantyl radical that is produced by the photoinduced decarboxylation could be trapped by alkenes or oxygen to deliver adducts or alcohols, respectively. The photodecarboxylation process was shown to be more efficient under acetone sensitization conditions (with quantum yields, Φ = 0.02–0.5) than upon direct excitation, and the reactivity was dependent on the chain length (intramolecular distance) between the electron donor (carboxylate) and acceptor (phthalimide in the triplet excited state) of the derivative. The formation of different radicals, that is, the 1‐ or 2‐adamantyl intermediate, probably does not affect the overall rate of the decarboxylation This current report provides a better understanding of photodecarboxylation and the rational design of molecular systems to undergo photoinduced decarboxylation and cyclization reactions.

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supporting

confidence: 86%

Section: Photochemical Reactivitymentioning

confidence: 99%

Section: Photochemical Reactivitymentioning

confidence: 99%

Section: Methyl 2-cyanoadamantane-1-carbamate (13me)mentioning

confidence: 99%

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Photodecarboxylation of Adamantane Amino Acids Activated by Phthalimide

et al. 2016

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“…The starting compound was 2-adamantyleneacetonitrile. The reduction REDUCTION OF UNSATURATED ADAMANTANE-CONTAINING NITRILES has been performed with either hydrogen over palladium under pressure (50 at) to give adamantan-2ylacetonitrile and reducing the latter with lithium aluminum hydride in tetrahydrofuran [9], or by lithium aluminum hydride in anhydrous tetrahydrofuran to give a mixture of 2-(adamant-2-yl)ethylamine and (2adamantylidene)ethylamine in a weight ratio of 7 : 3, respectively [10].…”

Section: Ia _ Ifmentioning

confidence: 99%

Reduction of unsaturated adamantane-containing nitriles

et al. 2015

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Antiproliferative and Antiviral Activity of Three Libraries of Adamantane Derivatives

Basarić

Sohora

Cindro

et al. 2014

Archiv der Pharmazie

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Three libraries of adamantane derivatives were synthesized and evaluated for antiviral and antiproliferative activities against a broad variety of DNA and RNA viruses. Whereas none of the compounds exhibit antiviral activity at subtoxic concentrations, antiproliferative activity was found against murine leukemia cells (L1210), human T-lymphocyte cells (CEM), and cervix carcinoma cells (HeLa) for 4, 8, and 10.

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Photoinduced hydrogen atom abstraction in N-(adamantyl)phthalimides: structure–reactivity study in the solid state

Cited by 21 publications

References 34 publications

Photodecarboxylation of Adamantane Amino Acids Activated by Phthalimide

Photodecarboxylation of Adamantane Amino Acids Activated by Phthalimide

Reduction of unsaturated adamantane-containing nitriles

Antiproliferative and Antiviral Activity of Three Libraries of Adamantane Derivatives

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