Polyfunctional fluoroalkyl-containing carbonyl compounds in the synthesis of heterocycles

Abstract

Efficient procedures for the regioselective synthesis of fluoroalkyl-containing three-, five-, six-, and seven-membered heterocycles as well as of related fused compounds, namely, ct,13-epoxyketones, ct,13-aziridinylketones, pyrazoles, pyrazolines, isoxazolines, 1,2-dithiolenes, amino-and mercaptopyrimidines, A3.~-2-thioxo-l,3,2-thiazaphosphorines, A~.5-2-thioxo -1,3,2-oxazaphosphorines, 2,3-dihydro-1,4-diazepines, azidno[ 1,2-a]quinoxalines, benzo[b]-and naphtho[2,3-bl-l,4-diazepines, and triazolopyridazines, which have been developed by the authors and coworkers, are summarized. The a-and It-functionalized fluoroalkylcontaining carbonyl compounds (13-diketones, 13-ketoesters, their salts, regioisomeric ~3-aminovinyl ketones, 13-aminovinylthiones, [3-hydroxyketones, a,[3-enones, and their halogen der-vatives) were used as synthons in the processes of formation of the above-mentioned heterocycles.

Metal and Boron Derivatives of Fluorinated Cyclic 1,3-Dicarbonyl Compounds

“…The solid residue was recrystallized from toluene to afford 2d as a grayishgreen powder, yield 0.80 g (71 %), m. p. 166. 5 …”

“…Fluorinated 1,3-dicarbonyls are of special importance in this context: their versatility, high reactivity and preparative availability make them often the starting compounds of choice [3 -5]. At the same time, fluorinated 1,3-dicarbonyl enolates (salts or complexes) [4 -7] give frequently better results, when compared to the related 1,3-dicarbonyl compounds, and are as a rule more convenient in handling [5,6,8]. In this paper we report the synthesis and several striking synthetic applications of metal derivatives of cyclic fluorinated 1,3-dicarbonyl compounds which were collected in our groups during studies in this field [9 -14].…”

Fluorinated lithium 1,3-diketonates as reagents to modify podands and crown-ethers

“…In this paper, we report on the synthesis of novel fluorinated enaminoketones as ligands bearing two coordination centers of different nature. It is worth noting that these compounds may not only be involved in heterocyclization reactions [4,11,12] which are widely used to obtain biologically active derivatives; they enhance penetration of such compounds through biological membranes due to the presence of both polyether's and fluorinated fragments [13,14].…”

“…Indeed, lithium b-diketonates 1 proved to be appropriate reagents for the synthesis of b-diketones metal-chelates, b-hydroxyketones, regioisomeric enaminoketones (b-aminovinylketones), as well as a variety of fluorinated heterocycles (izoxazoles, pyrazoles, pyrimidines, 1,4-diazepines, pyrazines, etc.) [1][2][3][4][5][6][7][8][9].…”

An Effective Borate-Mediated Approach to 1-Trifluoromethyl-1-hydroxy-3-ketophosphonates, Phosphinates, and Phosphine Oxides

“…13,18 A characteristic feature of the 1 H NMR spectra for phosphonates 4 and tertiary phosphine oxides 7 in CDCl 3 is the presence of an AB system of doublets at d = 2.7-3.6 ppm ( 2 J Ha-Hb = 15-19 Hz, 3 J Ha-P = 11- 17 Hz, 3 J Hb-P [2][3][4][5][6][7][8][9] for the methylene protons and doublet at d = 6.5-6.8 ppm ( The presence of a double bond in compounds 8-10 was confirmed by the appearance of a doublet of quartets at d = 7.5-7.7 ppm (J H-P = 31-39 Hz, J H-F = 1-2 Hz) and a doublet at d = 7.8-7.9 (J H-P [19][20][21][22][23][24] for olefinic protons of the major and the minor isomer in their 1 H NMR spectra, respectively. The Z configuration of the double bond in the predominant isomer was established uniquely since the range of the J H-P values is characteristic for trans position of hydrogen and phosphorus around a double bond.…”