Photodecarboxylation of Xanthone Acetic Acids:  C−C Bond Heterolysis from the Singlet Excited State

Blake, J. A.; Gagnon, Éric; Lukeman, Matthew; Scaiano, Juan C.

doi:10.1021/ol052953d

Cited by 49 publications

(54 citation statements)

References 15 publications

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“…This strategy, developed by Scaiano and co-workers, 375 is often based on the photochemical decarboxylation in the side-chain of a chromophore and is compatible with an aqueous environment. Benzophenone (LG = carboxylate; Φ < 0.7), 375a xanthone (LG = carboxylate; Φ < 0.7 376 ), 377 and phthalimide 378 moieties have been used as the chromophores.…”

Section: Miscellaneous Groupsmentioning

confidence: 99%

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

et al. 2012

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Section: Miscellaneous Groupsmentioning

confidence: 99%

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

et al. 2012

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“…Changes in the oxygen‐to‐carbon ratio of organic matter together with 13 C‐NMR data (Ward & Cory, ) give explicit evidence for the prominence of decarboxylation during photodegradation. This can occur when carboxylic acid groups are structurally close to the part of a molecule that absorbs radiation (e.g., Blake et al, ; Budac & Wan, ; Guzman et al, ; Schmitt‐Kopplin et al, ; Waggoner et al, ; Wang et al, ; Xu & Wan, ), with the aid of metal ions (e.g., Carraher et al, ; Faust & Zepp, ; Gao & Zepp, ; Gu et al, ; Miles & Brezonik, ), and in the presence of minerals (e.g., Miyoshi et al, ). These factors—structure of organic matter, metals, and minerals—likely determine the degree to which photodecarboxylation might occur in a soil.…”

Section: Discussionmentioning

confidence: 99%

Exposure to Light Elicits a Spectrum of Chemical Changes in Soil

2019

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The significance of photochemically active solar radiation is well substantiated in Earth's air and water environments, but no broad connection has yet been ascertained between sunlight and the chemical properties of land surfaces. Since it is obvious that sunlight strikes Earth every day, an inquiry into this connection was made in a simple experiment with a diverse group of 20 soils. Light‐induced alteration of most of the major elements in soil was evident, including significant changes in dissolved organic carbon, inorganic nitrogen, pH, phosphorus availability and sorption capacity, and soluble and mineral forms of iron, manganese, aluminum, silicon, and calcium. In many instances the extent of these changes could be predicted from initial values. This broad response to light attests to the vivid photochemistry of soils and has both pedological and edaphological implications that reach beyond the surface. The phenomena reported here affirm the opportunity for novel inquiries into the chemistry of soils and land surfaces in general.

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“…[9][10][11][12] Photocatalytic decarboxylation reactions have recently experienced a revival in organic synthesis, [13][14][15][16][17][18] and significant progress has been made to elucidate the photodecarboxylation reaction mechanism that leads to anionic species. [19][20][21][22][23][24][25][26][27][28] Photodecarboxylation can be initiated by the phthalimide chromophore in the triplet excited state, which acts as the electron acceptor in the photoinduced electron transfer (PET) reaction. [29,30] The PET-promoted decarboxylation by phthalimides has been used in macrocyclizations, [31] the cyclization of peptides, [32,33] photodecaging strategies, [34] and the enantioselective synthesis of benzodiazepines.…”

Section: Introductionmentioning

confidence: 99%

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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Photodecarboxylation of Xanthone Acetic Acids: C−C Bond Heterolysis from the Singlet Excited State

Cited by 49 publications

References 15 publications

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

Photoremovable Protecting Groups in Chemistry and Biology: Reaction Mechanisms and Efficacy

Exposure to Light Elicits a Spectrum of Chemical Changes in Soil

Photodecarboxylation of Adamantane Amino Acids Activated by Phthalimide

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