TFBen (Benzene‐1,3,5‐triyl triformate): A Powerful and Versatile CO Surrogate

Abstract

Carbonylative reactions by the using of CO surrogates constitute a facile avenue for the assembly of valuable carbonyl-containing compounds due to the colorless, toxic, flammable, and not easy-handing character of carbon monoxide gas. Recent advances in the carbonylative transformations with TFBen (benzene-1,3,5-triyl triformate) as a safe and convenient CO precursor are systematically summarized and discussed, which can be divided into three parts based on the patterns of the obtained products. This Review focuses on the discussion of the application of TFBen in carbonylative synthesis of various carbonyl-containing compounds.

Formic Acid as Carbon Monoxide Source in the Palladium-Catalyzed N-Heterocyclization of o-Nitrostyrenes to Indoles

“…This problem is not limited to N-heterocyclization reactions but is a common issue for many synthetic protocols for fine chemical production in which CO is employed. A shared problem is a halved problem; thus, researchers developed alternative methods in which molecules (CO surrogates) able to release CO under the reaction conditions are used instead of pressurized CO. 17 In this context, Mo(CO) 6 , 18 aryl formates, 19 and CO 2 /silanes 20 have been used in the synthesis of indoles and related five-membered ring heterocycles from nitro compounds ( Scheme 1 d). Drawbacks to the use of surrogates are in some cases the relatively high cost, the toxicity of some compounds, the need for specific multichamber reactors, or the difficult separation from the product.…”

Metal-free synthesis of 3-trifluoromethyl-1,2,4-triazoles via multi-component reaction of trifluoroacetimidoyl chlorides, hydrazine hydrate and benzene-1,3,5-triyl triformate

“…Benzene-1,3,5-triyl triformate (TFBen) is first designed and developed by Wu and co-workers and has usually been used as a potent CO surrogate in diverse carbonylative transformations ( Jiang, et al, 2016 ; Yang, et al, 2022 ). Meanwhile, TFBen is also adopted as a C1 source in the formation of a variety of heterocycles.…”

Palladium-Catalyzed Cascade Carbonylative Synthesis of Perfluoroalkyl and Carbonyl-Containing 3,4-Dihydroquinolin-2(1H)-one Derivatives

“…Enlightened by previous reports on radical cascade reactions and our recent efforts on carbonylation reactions, we would like to report here our study on palladium-catalyzed cascade radical cyclization and carbonylation of 1,7-enynes with perfluoroalkyl iodides. Using TFBen as the CO source, a variety of perfluoroalkyl and carbonyl-containing 3,4-dihydroquinolin-2(1 H )-one derivatives were produced in high yields and with excellent E / Z selectivity.…”