A novel and practical decarboxylative alkynylation of α-keto acids with bromoacetylenes is catalyzed by hypervalent iodine(III) reagents when irradiation by sunlight at room temperature. The product ynones are generated in good yields. Experiments show that results obtained with blue light (λ=450-455 nm) are comparable to those obtained when using sunlight. Mechanistic studies demonstrate that the sunlight-driven decarboxylation undergoes a radical process.

A hypervalent iodine(iii) reagent catalyzed carbonylarylation of acrylamides with α-oxocarboxylic acids driven by visible-light without a photoredox catalyst has been developed. The reactions generate the corresponding products in good yields at room temperature. Experiments indicate that a blue LED (450-455 nm) is the most effective energy for the cleavage of the oxygen-iodine bond to initiate the reaction. Mechanistic studies further demonstrate that the reaction undergoes a cascade decarboxylative radical addition/cyclization process along with releasing CO2 and H2.

A highly enantioselective palladium/WJ-Phos-catalyzed Suzuki−Miyaura coupling reaction for efficient construction of axially chiral biaryl monophosphine oxides was developed. A series of axially chiral biaryl monophosphine oxides were obtained in good yields and with high enantioselectivities. The practicability of this reaction was validated in the straightforward synthesis of axially chiral biaryl monophosphine ligand and demonstrated by a 100-g-scale synthesis. Moreover, various functionalizations of the product make it as a platform molecule for synthesis of other chiral biaryl phosphines.

No Abstractmagnified image

Visible-light-induced oxidative formylation of N-alkyl-N-(prop-2-yn-1-yl)anilines with molecular oxygen in the absence of an external photosensitizer was developed and afforded the corresponding formamides in good yields under mild conditions. The investigation of the mechanism disclosed that both the starting material and the product act as photosensitizers, and O and O˙ are generated through energy transfer and a single electron transfer pathway and play an important role in the reaction.

An ovel and practical decarboxylative alkynylation of a-keto acids with bromoacetylenes is catalyzedb yh ypervalent iodine(III) reagents when irradiation by sunlight at room temperature.The product ynones are generated in good yields.E xperiments show that results obtained with blue light (l = 450-455 nm) are comparable to those obtained when using sunlight. Mechanistic studies demonstrate that the sunlight-driven decarboxylation undergoes ar adical process.

A novel, simple, effective and rapid synthetic method to construct the corresponding C-2 trifluoromethylated indolinyl ketones via a copper-catalyzed cyclization reaction between N-alkylaniline and -(trifluoromethyl)-α,-unsaturated enones was developed. The control...

Ynones. -(TAN, H.; LI*, H.; JI, W.; WANG, L.; Angew. Chem., Int. Ed. 54 (2015) 29, 8374-8377, http://dx.