Sustainable, cobalt-catalyst enabled, synthetically significant CÀF/CÀHf unctionalizations were achieved with an ample substrate scope at an ambientt emperature of 25 8C, thereby delivering perfluoroallylated heteroarenes. Detailed experimental and computational mechanistic studies on the CÀF/CÀHf unctionalizations provided strong support for af acile CÀFcleavage.CÀHf unctionalizations have been recognized asi ncreasingly viable tools for molecular synthesis, [1] with applications in material sciences, [2] as well as the agrochemical and pharmaceutical industries.[3] As ignificant advance was recently made by Loh, Li, Wang,a nd Ackermann, in whichC ÀHa ctivation chemistry was merged with challenging CÀFf unctionalizations within aC ÀF/CÀHa ctivation manifold, [4] thereby providing access to selectively fluorinated molecules.[5] Despite these undisputed advances, catalytic CÀF/CÀHf unctionalizations continue to be scarce, and are limited to elevated reaction temperatures and/or strongly nucleophilic hydroxide bases, which considerably compromise chemoselectivity.I nc ontrast, within our program on sustainable CÀHf unctionalizations, [6] we have now developed af irst room-temperature CÀF/CÀHf unctionalization using earth-abundant cobalt catalysis, [7][8][9] with the weak base K 2 CO 3 under exceedingly mild reaction conditions (Figure 1). Notable features of our findings include (i)C ÀF/CÀH functionalizations at room temperature withm ild carbonate bases, (ii)first cobalt-catalyzed CÀF/CÀHa llylations with perfluoroalkyl alkenes, (iii)C ÀF/CÀHf unctionalizations with cobalt loadings as low as 0.25 mol %, and (iv) detailed mechanistic insights into the working mode of CÀF/CÀHf unctionalization by cobalt catalysis.We initiated our studies by probing the effect exertedbydifferent solvents and weak bases on the unprecedented cobaltcatalyzed CÀF/CÀHf unctionalization of indole 1a with perfluoroalkylalkene 2a (Table 1and Ta ble S1 in the Supporting Information). Indeed, the desired CÀF/CÀHt ransformation provedv iable,p articularly when using TFE as the most effective solvent( entries 1-4). Amongavariety of weak bases, K 2 CO 3 turned out to be optimal (entries 4-14). Notably,t he

A novel domino reduction/imine formation/intramolecular cyclization/oxidation for the efficient synthesis of pyrrolo(indolo)[1,2-a]quinoxalines and pyrrolo(indolo)[3,2-c]-quinolines from readily available nitrobenzenes and glycols is reported. The process utilizes the carbonyl byproduct of the initial dioxomolybdenum(VI)-catalyzed reduction of nitroaromatics with glycols as a reagent for the imine generation. This method represents the first sustainable domino reaction for the preparation of biologically relevant heterocycles that internally incorporates the waste formed in the first step to the final product.

An efficient and eco-friendly oxidative cleavage of glycols using DMSO as an oxidant catalyzed by dioxomolybdenum(vi) complexes has been developed.

A molybdenum-catalyzed deoxygenation of pyridine N-oxides and N-hydroxybenzotriazoles, as well as other azole N-oxides, has been developed using pinacol as an environmentally friendly oxoacceptor. The only by-products are acetone and water making the process a convenient alternative to established protocols in terms of waste generation. The reaction is highly chemoselective and a variety of functional groups are tolerated. The processes are usually very clean allowing the isolation of the pure deoxygenated products after a simple extraction in most cases.

Polysubstituted quinolines have been efficiently synthesized from nitroarenes and glycols, as reducing agents, under dioxomolybdenum(VI)catalysis. Interestingly, the waste reduction byproduct is incorporated into the final heterocycle. This method represents an efficient and sustainable variant of the Friedlä nder synthesis of quinolines.