Fluoroalkyl derivatives

Welch MJ, Chi DY, Mathias CJ, Kilboum MR, Brodack JW, Katzenel-lenbogen JA. Biodistribution of A-alkyl and TV-fluoroalkyl derivatives of spiroperidol radiopharmaceuticals for PET studies of dopamine receptors. Appl Radiat Isot 1986 13 523-526. 

A. Torrisi, N. Tuccitto, G. Maccarrone and A. Licciardello, ToF SIMS characterization of fluoroalkyl derivatives of possible interest as water repellent for stone protection, Appl. Surf. Sci., 255, 1527 1530 (2008). 

N. Truong Thi Thanh, C. Menage, J.P. Begue, D. Bonnet-Delpon, J.C. Gantier, B. Pradines, J.C. Doury, T. Truong Dinh, Synthesis and antimalarial activities of fluoroalkyl derivatives of dihydroartemisinin, J. Med. Chem. 41 (1998) 4101-4108. 

Some other fluoroalkyl derivatives of silicon (e.g., ArCF2TMS, CICF2TMS, RfTMS, CeFsTMS) have been prepared and used as fluoroalkylating reagents. Unfortunately, their reactivity is much lower than that of CF3TMS, and they have not found important synthetic applications. " ... 

Numerous S -fluoroaryl or S -fluoroalkyl derivatives of cysteine have been described. Thus, fluorination of S -benzyl cysteine has been performed with XeFa- The photochemical trifluoromethylation of cysteine, or of its disulfide, affords optically pure S -trifluoromethyl cysteine. Some electrophilic halogenated compounds (such as trifluorochloroethylene) are able to achieve the 5-fluoroalkylation of cysteine. 

S -Mono-, di-, and trifluoro derivatives of methionine and 5-fluoroalkyl derivatives of cysteine are accessible through fluorination. Thus, fluorination of methionine sulfoxide with xenon fluoride, or more easily using DAST, provided 5-monofluor-omethionine. Photochemical trifluoromethylation of homocysteine leads to 5-trifluoromethionine. These S -fluoroalkyl compounds are also available through fluoroalkylation of homocysteine. Thus, the addition of difluorocarbene (formed from Freon 11 (CHF2CI)) affords S -difluoromethionine. ... 

Figure 6.51 Fluoroalkyl derivatives of AFacetylmuramyl-L-alanyl-D-isoglutamine.

K. Thomas, J. A. Osborn, A. R. Powell, and G. Wilkinson, The Preparation of Hydridopentammine- and Hydridoaquotetraammine-rhodium(III) Sulfates and Other Salts the Formation of Alkyl and Fluoroalkyl Derivatives, J. Chem. Soc. A 1968, 1801-1806. 

Only 2-fluoroalkyl derivatives 573 were obtained when pyrrole and indole were treated with per(poly)fluoroalkyl chlorides (RpCl) in the presence of sodium dithionite in DMSO (Equation 137) <2001JEC(111)107>. 

Since the direct synthesis of alkylchlorosilanes has enabled the industrial development of silicones, a-fluoroalkyl derivatives were also given some attention because perfluorosilicones presumably could combine the outstanding properties of both conventional silicones and perfluorocarbon polymers [1]. 

Insertion of alkynes and perfluoroalkenes into the Re-H bond of (31) allows the preparation of /3-hydrogen-substituted vinyl and fluoroalkyl derivatives, Re C(CF3)=CH(CF3) (CO)5 and Re(CF2CHF2)(CO)s. 

Peptide Fluoromethyl Ketones Fluoroalkyl derivatives of the peptide chloromethyl ketones have been prepared in an attempt to improve specificity by reducing nonspecific alkylation at cysteine residues (Rasnick, D., Synthesis of peptide fluoromethyl ketones and the inhibition of human cathepsin B, Anal. Biochem. 149, 461 65, 1985). Nonspecific reaction with sulfydryl groups such as those in glutathione was reduced there was still reaction with active site cysteine although at a slower rate than with the chloroalkyl derivative (16,200 M s vs. 45,300 1 2 21.9 min. vs. 

Tris- and tetrakis (triphenylphosphine) platinum (0) are the source of many platinum compounds. They react with carbon monoxide, acids/ methyl iodide/ fluoroalkyl derivatives/ carbon disulfide/ oxygen/ chloro/ fluoro/ and activated olefins/ hydrogen sulfide and selenide/ and sulfur dioxide/ yielding many platinum (II) or platinum (0) compounds which cannot be obtained easily by other routes. 

So far as possible, the same order has been used for the fluoroalkyl derivatives in each group of transition metals a-bonded alkyl, alkenyl, and alkynyl derivatives, 7r-bonded derivatives, and then derivatives bonded via N, P, O, or S in that order. In some cases, notably olefin complexes, there is ambiguity about the bonding and this should be borne in mind when searching for particular compounds. Fluoroaryl and heteroaryl derivatives form a more homogeneous group of compounds, and their parameters are considered together across the transition series. 

II. FLUOROALKYL DERIVATIVES A. Groups Illb-Vb, including the lanthanides and actinides... 

The preparation of a series of fluoroalkyl derivatives of the Co3(CO)9C cluster has been reported, and parameters are given with structure [193]. (82) The bright red product formed in low yield in the reaction of (CF3)2CFCo(CO)4 with NaCo(CO)4 is thought from its 19F NMR spectrum (sharp singlet, <5 -43-5) and other properties to be (CO)3Co(CO)[C(CF3)2]Co(CO)3. 

FITS reagents reacted with various carbanions to afford under mild conditions the corresponding fluoroalkylated derivatives. The yields are quite dependent upon the nature of the carbanion and of the counterion. (Table 5.9)... 

Stability, but the origin of this behavior is still unknown. One possible explanation involves the close-packing nature of fluorined side chains, which may provide a kinetic barrier to oxidation. Asymmetric NTCDIs with alkyl and fluoroalkyl sidechains have also been synthesized (46i-461). The highest mobility obtained with an alkyl version (46i) was 3 x 10" cm V s under vacuum and 2 x 10" cm V s with a fluoroalkyl derivative (46j).[271]... 

Fluoro-5-(fluoroalkyl) derivatives 160 are synthesized from the corresponding ketene dithioacetals 161 (Scheme 35) [85,86]. The 4,5-bis(methoxy-... 

The most commonly used shift reagents are based on europium (downfield shifts) and praseodymium (upheld shifts) and contain either dipivaloyl methane (Ri = Ra = r-butyl, Rg = H) or fluoroalkyl derivatives of jS-diketones as ligands. 

A C02-philic rhodium catalyst was generated using the para-subsituted fluoroalkyl derivative of triphenylphosphine, 4-H F -TPP (2). Emulsion-type mixtures were formed under the reaction conditions upon stirring, but the two layers separated rapidly when stirring was stopped. Complete conversion to aldehyde was obtained in 20 h using a rhodium/phosphine/substrate ratio of 1 10 500. The catalyst was recycled three times without any loss of activity and without the requirement of expansion/recompression of the CO2 phase, giving a total turnover number of nearly 1500 in three consecutive runs. 

Be(/3-dik)2] and [B(j3-dik)a] species. The -diketones involved included various alkyl, aryl, and fluoroalkyl derivatives. ... 

The only main group derivatives in which NMR appears to have played a role in structure determination are the CF3BF3- anion 54) and in the fluoroalkyl derivatives of tin 64). For CF3BF3, the spectrum revealed coupling... 

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