Decarboxylative iodination: a convenient synthesis of bridgehead iodides

Abeywickrema, Ramyani S.; Della, Ernest W.

doi:10.1021/jo01309a034

Cited by 24 publications

(9 citation statements)

References 3 publications

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“…N-Protected piperidine iodides, such as N-tert-butoxycarbonyl (16), benzyloxycarbonyl (17,19) and benzoyl (18,20), were obtained in good yields. Both cyclic and acyclic secondary carboxylic acid-derived RAEs reacted well (14)(15)(16)(17)(18)(19)(20)(21)(22). For the reaction leading to 21, the byproduct of intramolecular radical cyclization on the ortho-C-H of phenyl was detected.…”

Section: Introductionmentioning

confidence: 99%

“…Notably, a recent report by Larrosa et al delineated an efficient transition-metal-free iododecarboxylation of arene carboxylic acid using molecular iodine. Reported examples of iododecarboxylation of aliphatic carboxylic acid derivatives include halogenative decarboxylation of Barton esters with iodoform, oxidative methods using PhI(OAc) 2 /I 2 or N -iodoamides under light, decarboxylation of bridgehead carboxylic acid with t -BuOCl and HgI 2 , and a recent photoredox method using iridium photoredox catalyst and N -iodosuccinimide . The propensity of iodine cations to undergo electrophilic substitution with arenes presents another challenge in chemoselective iododecarboxylation for complex molecules containing electron-rich arene moieties .…”

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confidence: 99%

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Triphenylphosphine-Catalyzed Alkylative Iododecarboxylation with Lithium Iodide under Visible Light

Wang

Shang

2020

Org. Lett.

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Photoactivation of an electron donor-acceptor encounter complex in an organic solvent cage, a phenomenon that has been described in Mulliken theory, has been known for decades, but it has not been employed as a photoactivation step in the design of photocatalysis for organic synthesis until recent years. We report herein an iododecarboxylation reaction that applies this concept for photoactivation by using a catalyst to facilitate electron transfer and to suppress back electron transfer in the photoexcited state. Under irradiation of 456 nm blue light-emitting diodes, PPh3 catalyzes the iododecarboxylation of aliphatic carboxylic acid-derived N-(acyloxy)phthalimide with lithium iodide as iodine source. The reaction delivers primary, secondary, and bridgehead tertiary alkyl iodides in acetone solvent, and the alkyl iodide products were easily used to generate C-N, CO , C-F, and C-S bonds to allow various decarboxylative transformations without using transition-metal or organic dye-based photocatalysts. This protocol is applicable to redox-active esters derived from various natural products and pharmaceuticals.

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Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

Triphenylphosphine-Catalyzed Alkylative Iododecarboxylation with Lithium Iodide under Visible Light

Wang

Shang

2020

Org. Lett.

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Section: Introductionmentioning

confidence: 99%

Triphenylphosphine-catalyzed Alkylative Iododecarboxylation with Lithium Iodide under Visible Light

Wang

Shang

2020

Preprint

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Photoactivation of an electron donor–acceptor encounter complex in an organic solvent cage, a phenomenon that has been described in Mulliken theory, has been known for decades, but it has not been employed as a photoactivation step in the design of photocatalysis for organic synthesis until recent years. We report herein an iododecarboxylation reaction that applies this concept for photoactivation by using a catalyst to facilitate electron transfer and to suppress back electron transfer in the photoexcited state. Under irradiation of 456 nm blue light-emitting diodes, PPh3 catalyzes the iododecarboxylation of aliphatic carboxylic acid-derived N-(acyloxy)phthalimide with lithium iodide as iodine source. The reaction delivers primary, secondary, and bridgehead tertiary alkyl iodides in acetone solvent, and the alkyl iodide products were easily used to generate C–N, C–O, C–F, and C–S bonds to allow various decarboxylative transformations without using transition-metal or organic dye-based photocatalysts. This protocol is applicable to redox-active esters derived from various natural products and pharmaceuticals.

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“…[13,14] Other examples of decarboxylative radical-based methods have been reported. [15,16] The synthesis of alkoxy cubanes 7 has been reported from iodides 6, which are again accessed from cubane carboxylic acids, [17][18][19] or their pyridyl esters. [20,21] Eaton and co-workers reported that photolysis of a dilute (0.03 m) solution of 1,4-diiodocubane in methanol afforded 1-iodo-4-methoxycubane in 10 % yield.…”

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confidence: 99%

Cubane Electrochemistry: Direct Conversion of Cubane Carboxylic Acids to Alkoxy Cubanes Using the Hofer–Moest Reaction under Flow Conditions

Collin

Folgueiras‐Amador

Pletcher

et al. 2019

Chemistry A European J

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The highly strained cubane system is of great interest as a scaffold and rigid linker in both pharmaceutical and materials chemistry. The first electrochemical functionalisation of cubane by oxidative decarboxylative ether formation (Hofer–Moest reaction) was demonstrated. The mild conditions are compatible with the presence of other oxidisable functional groups, and the use of flow electrochemical conditions allows straightforward upscaling.

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Decarboxylative iodination: a convenient synthesis of bridgehead iodides

Cited by 24 publications

References 3 publications

Triphenylphosphine-Catalyzed Alkylative Iododecarboxylation with Lithium Iodide under Visible Light

Triphenylphosphine-Catalyzed Alkylative Iododecarboxylation with Lithium Iodide under Visible Light

Triphenylphosphine-catalyzed Alkylative Iododecarboxylation with Lithium Iodide under Visible Light

Cubane Electrochemistry: Direct Conversion of Cubane Carboxylic Acids to Alkoxy Cubanes Using the Hofer–Moest Reaction under Flow Conditions

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