2021
DOI: 10.1038/s41467-021-23101-3
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Chemoselective catalytic hydrodefluorination of trifluoromethylalkenes towards mono-/gem-di-fluoroalkenes under metal-free conditions

Abstract: Fluorine-containing moieties show significant effects in improving the properties of functional molecules. Consequently, efficient methods for installing them into target compounds are in great demand, especially those enabled by metal-free catalysis. Here we show a diazaphospholene-catalyzed hydrodefluorination of trifluoromethylalkenes to chemoselectively construct gem-difluoroalkenes and terminal monofluoroalkenes by simple adjustment of the reactant stoichiometry. This metal-free hydrodefluorination featur… Show more

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Cited by 72 publications
(48 citation statements)
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“…15,16 The reduction of 5f with Red-Al afforded monofluoroalkene 5fd with excellent Z / E selectivity. 17…”
Section: Resultsmentioning
confidence: 99%
“…15,16 The reduction of 5f with Red-Al afforded monofluoroalkene 5fd with excellent Z / E selectivity. 17…”
Section: Resultsmentioning
confidence: 99%
“…These defluorination transformations do not appear to involve radical chemistry. [19,20] PhSiH 3 and HB(pin) are not directly reactive with 3 in acetonitrile, unlike the DAP fluoride. [21] DAP chlorides and bromides are reduced to 1 using LiAlH 4 or Red-Al, [1] but these reductants are incompatible with acetonitrile, require cooling, produce significant phosphine (PH 3 ) byproduct, and give modest yields of 1, making them unsuitable as terminal reductants catalytic reactions at room-temperature.…”
Section: Stoichiometric Reductive Chemistry With Diazaphospholenesmentioning
confidence: 99%
“…These defluorination transformations do not appear to involve radical chemistry. [19,20] PhSiH 3 and HB(pin) are not directly reactive with 3 in acetonitrile, unlike the DAP fluoride. [21] DAP chlorides and bromides are reduced to 1 using LiAlH 4 or Red-Al, [1] but these reductants are incompatible with acetonitrile, require cooling, produce significant phosphine (PH 3 ) byproduct, and give modest yields of 1, making them unsuitable as terminal reductants in catalytic reactions at room-temperature.…”
Section: Stoichiometric Reductive Chemistry With Diazaphospholenesmentioning
confidence: 99%
“…A cinnamyl thioether underwent clean conversion to form 8 f. The cyclization of substrates containing aryl fluorides to form 8 g and 8 h were successful, with no defluorination observed. [20] Two isomeric trifluoromethyl containing cinnamyl ethers also underwent cyclization to form 8 i and 8 j without defluorination. Nitrile containing ethers underwent cyclization to form 8 k and 8 l, and ester groups were similarly tolerated to give 8 m and 8 n. A terminal allyl ether cyclized with high conversion to give 8 o but small amounts of what we suspected were the 6-endo cyclization mode were noted.…”
Section: Stoichiometric Reductive Chemistry With Diazaphospholenesmentioning
confidence: 99%