An efficient and expeditious synthesis of functionalized trifluoromethyl ketones through lithium-iodine exchange reaction

Villuendas, Isabel; Parrilla, A.; Guerrero, Ángel

doi:10.1016/s0040-4020(01)89400-x

Cited by 26 publications

(22 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Compounds 1 and 5 were prepared as already reported by us [30, 31], and the synthesis of compounds 2 [12] and 3 [32] has been already described. Compounds 6 and 7 were obtained from n -decanal and n -octanamide, respectively (manuscript in preparation).…”

Section: Methodsmentioning

confidence: 99%

“…Compounds 11 – 13 were taken from ref [28]. TFMKs 14 , 16 and 17 were prepared by trans -metallation reaction of the corresponding iododerivatives with tert -BuLi followed by treatment with ethyl trifluoroacetate [31]. Compound 15 was synthesized from 1-octadecene with trifluoroacetaldehyde ethyl hemiacetal in the presence of a Lewis acid followed by Dess-Martin oxidation [34] of the resulting trifluoromethyl carbinol (submitted for publication).…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Reactivity versus steric effects in fluorinated ketones as esterase inhibitors: a quantum mechanical and molecular dynamics study

et al. 2010

Self Cite

View full text Add to dashboard Cite

Carboxylesterases (CEs) are a family of ubiquitous enzymes with broad substrate specificity, and their inhibition may have important implications in pharmaceutical and agrochemical fields. One of the most potent inhibitors both for mammalian and insect CEs are trifluoromethyl ketones (TFMKs), but the mechanism of action of these chemicals is not completely understood. This study examines the balance between reactivity versus steric effects in modulating the activity against human carboxylesterase 1. The intrinsic reactivity of the ketone moiety is determined from quantum mechanical computations, which combine gas phase B3LYP calculations with hydration free energies estimated with the IEF/MST model. In addition, docking and molecular dynamics simulations are used to explore the binding mode of the inhibitors along the deep gorge that delineates the binding site. The results point out that the activity largely depends on the nature of the fluorinated ketone, since the activity is modulated by the balance between the intrinsic electrophilicity of the carbonyl carbon atom and the ratio between keto and hydrate forms. However, the results also suggest that the correct alignment of the alkyl chain in the binding site can exert a large influence on the inhibitory activity, as this effect seems to override the intrinsic reactivity features of the fluorinated ketone. Overall, the results sustain a subtle balance between reactivity and steric effects in modulating the inhibitory activity of TFMK inhibitors.

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Reactivity versus steric effects in fluorinated ketones as esterase inhibitors: a quantum mechanical and molecular dynamics study

et al. 2010

Self Cite

View full text Add to dashboard Cite

show abstract

“…Z11‐16:TFMK was synthesized as previously reported 8. Z11‐16:Ac, free from the corresponding alcohol, was prepared in the laboratory and purified by HPLC.…”

Section: Methodsmentioning

confidence: 99%

“…Specific applications of the latter substances to the inhibition of the insect olfaction process have been reported 6. 7 Thus, pheromone analogues bearing a trifluoromethyl ketone function have been synthesized8, 9 and their biological activity evaluated 9–11. In this regard, Bau et al 12 demonstrated for the first time that several TFMK analogues topically applied to the antennae disrupt the upwind flight of males to pheromone sources in a wind tunnel in two moth species, the Egyptian armyworm, Spodoptera littoralis Boisd, and the Mediterranean corn borer, Sesamia nonagrioides Lef ( Sesamia calamistis Hamps).…”

Section: Introductionmentioning

confidence: 99%

Disruption of responses to pheromone by (Z)‐11‐hexadecenyl trifluoromethyl ketone, an analogue of the pheromone, in the cabbage armyworm Mamestra brassicae

Renou

Berthier

Guerrero

2002

Pest Management Science

Self Cite

View full text Add to dashboard Cite

The effects of (Z)-11-hexadecenyl trifluoromethyl ketone (Z11-16:TFMK) a fluorinated pheromone analogue, on the responses to sex pheromone of the male cabbage armyworm, Mamestra brassicae, have been investigated in an actograph and by electroantennography (EAG). In spite of its structural proximity with the natural pheromone, Z11-16:TFMK was poorly active in EAG, and not active on male behaviour. When permeated in the air, Z11-16:TFMK reversibly inhibited the electroantennographic responses to (Z)-11-hexadecenyl acetate (Z11-16:Ac), the main component of the sex pheromone. In the actograph, the latency of the activation was increased and the intensity of the behavioural activity of males in response to Z11-16:Ac was significantly reduced in the presence of Z11-16:TFMK. These results, along with others previously reported by us, provide new pointers to the possible use of Z11-16:TFMK in pest-control strategies.

show abstract

“…The low reaction yield made further synthesis impractical. We improved the synthesis of 1 by the reaction of C 6 F 13 C 2 H 4 I with t-BuLi, according to a literature procedure [14], followed by reaction with HSiCl 3 (Scheme 1). This method was very efficient and a 95% conversion of the organolithium intermediate was achieved.…”

Section: Synthesis Of Polyfluoroalkylsilanementioning

confidence: 99%

Synthesis and fluxional behaviour of new “heavy fluorous” cyclopentadienes

Šťastná

Čermák

Cuřínová

et al. 2010

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

An efficient and expeditious synthesis of functionalized trifluoromethyl ketones through lithium-iodine exchange reaction

Cited by 26 publications

References 34 publications

Reactivity versus steric effects in fluorinated ketones as esterase inhibitors: a quantum mechanical and molecular dynamics study

Reactivity versus steric effects in fluorinated ketones as esterase inhibitors: a quantum mechanical and molecular dynamics study

Disruption of responses to pheromone by (Z)‐11‐hexadecenyl trifluoromethyl ketone, an analogue of the pheromone, in the cabbage armyworm Mamestra brassicae

Synthesis and fluxional behaviour of new “heavy fluorous” cyclopentadienes

Contact Info

Product

Resources

About