Catalytic Aerobic Photooxidative Cleavage of Carbon-Carbon Triple Bonds Using Carbon Tetrabromide

Abstract

We developed the aerobic photooxidative cleavage of carbon-carbon triple bonds to carboxylic acids in the presence of catalytic amounts of carbon tetrabromide under photoirradiation with a high-pressure mercury lamp.

Synthesis of Aryl Carboxylic Acids through Ambient Electro-oxidation of Arylacetylenes

“…17 Among various applications of these methods in the traditional syntheses, the oxidation of alkynes was not investigated very well. A successful example was that of Itoh’s group 18 who obtained the carboxylic acids from the alkynes by a photochemistry method with carbon tetrabromide (CBr 4 ) as the catalyst and a high-pressure mercury lamp as the light source. In the most recently reported work by Huang’s group, 19 an electrochemical method for the oxidation of terminal alkynes to the carboxylic acids was described, in which acetic acid was used as additive and sodium nitrite as trifunctional reagent, but long reaction time was required.…”

Applications of Photoredox Catalysis for the Radical-Induced Cleavage of C–C Bonds

“…The report from Itoh in 2013 on the aerobic photo-oxidative cleavage of carbon-carbon triple bonds was the result of a follow-up study about their work on the C=C bond cleavage using CBr4 as the catalyst under photoirradiation. 83 In that case, various olefins were converted to their respective aldehyde (or ketone) product. 50 In their work from 2013, however, the use of alkynes as substrates allowed for the synthesis of carboxylic acids.…”

“…In 2013, the Itoh group reported the aerobic photo-oxidative cleavage of C≡C bonds; 83 this was a follow-up study to their work on C=C bond cleavage in various olefins using CBr 4 as the catalyst under photoirradiation to give aldehyde (or ketone) products (Section 3.1). 51 The use of alkynes as substrates under these conditions allowed the synthesis of carboxylic acids.…”

Triplet Excited Nitroarene Converts Linear Alkynes to Bent Ketones by Deleting a Carbon Atom

“…13 The ozonolysis of alkynes gave mixtures of products, with the precise composition of these products being influenced by both the reaction conditions and the electronic characteristics of the substrate (Figure 1c). The cleavage of alkynes has been reported with stoichiometric transition metal oxides, 14 hypervalent iodine, 15 peracids, 16 and pressurized molecular oxygen 17 . A previous reaction of alkynes with photoexcited nitrobenzene under mercury arc lamp irradiation for three days produced a mixture of benzophenone-anil, carbon dioxide, https://doi.org/10.26434/chemrxiv-2023-t1cvq-v2 ORCID: https://orcid.org/0000-0001-5034-423X Content not peer-reviewed by ChemRxiv.…”