Photofluorination with fluoroxytrifluoromethane, a general method for the synthesis of organic fluorine compounds. Direct fluorination of bioactive molecules

Abstract

Photofluorination with Fluoroxytrifluoromethane, a General Method for the Synthesis of Organic Fluorine Compounds. Direct Fluorination of Bioactive Molecules

Stereoselectively fluorinated N-heterocycles: a brief survey

“…However, this transformation can be a very effective and concise method for synthesising fluorinated N -heterocycles. For example, L- cis -3-fluoroazetidine-2-carboxylic acid ( 73 ) was synthesised in one step from the corresponding amino acid 72 by photofluorination with fluoroxytrifluoromethane as the source of the fluorine radical, in 53% yield [ 72 ] ( Scheme 9 ).…”

Novel trialkoxymethyl disulfides via nucleophilic addition to thionocarbonates: tris(2-fluoro-2,2-dinitroethoxy)methyl trichloromethyl disulfide and related products

“…Another possible mechanism for the formation of 3 would be cleavage of 2 into ions followed by combination with tris(fluorodinitroethoxy)methanethiolate ion.6 If the alkoxide used to attack the thionocarbonate is different from the substituents in the thionocarbonate the (4) See ref 7. (5) Subsequent to submission of this article but prior to receiving the reviewer's comments we considered this mechanism and performed the necessary experiments. However, we thank the reviewer for also suggesting this possibility.…”

“…This transformation occurs in greater than 95% yield when a dichloroethane solution of the disulfide is treated with gaseous chlorine at 60 °C for 4 h or at ambient temperature for 7 h (eq 5). The preparation of the chloroorthoformates C1CH2CH2C1 2 + Cl2 --[FC(N02)2CH20]3CC1 (5) as well as numerous derivatives prepared from them will be described in a subsequent paper.10…”

Reactions of naphthalene and anthracene derivatives with trifluoromethyl hypofluorite

“…The cooled petroleum ether solution furnished 0.55 g (43%) of l,l-difluoro-2-naphthone (3) as pale yellow needles, mp 49-50.5°. Sublimation at 40°(0.5 mm) furnished pure 3 with little loss of material: mp 50.5-52°; ir (melt between salt plates) 1700 cm"1 (C=0); nmr (CCU) 6.12 (two sets of triplets, 1 H, C=CHC=0, Jh-h = 10, Jh-f = 2.8 Hz), 7.31-7.99 (m, 5 H, aromatic and CH=CCDO).…”