Synthesis of Fluoromonoterpenoids as potential suicide substrates for plant cells

Banthorpe, D. V.; Ireland, M. J.

doi:10.1002/prac.19963380154

Cited by 10 publications

(7 citation statements)

References 25 publications

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“…d, J = 4.9, C5),17.9; data are in accord with literature values[4].19 F NMR (376 MHz, CDCl 3 , Teflon insert, 22 8C):d À148.5 (m, 3 J H4-F = 23.3, 3 J C(3)CH-F = 21.1, 3 J H2-F = 18.3, 3 J H4 0 -F = 16.6). After 18d 13 h of thermolysis, 1 H and 19 F NMR spectra showed formation of 4-(1-fluoro-1-methylethyl)-1-methylcyclohexene (a-terpinyl fluoride, 12), in 60% yield by 19 F NMR integration.…”

supporting

confidence: 89%

On the isolation of neat allylic fluorides

Lee

Yandulov

2009

Journal of Fluorine Chemistry

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supporting

confidence: 89%

On the isolation of neat allylic fluorides

Lee

Yandulov

2009

Journal of Fluorine Chemistry

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“…Colorless liquid; bp10 46 °C; 1 H NMR δ 0.10 (s, 9H), 0.15 (s, 9H), 1.40 (s, 3H); 19 F NMR δ -76.5 (s); 13 C NMR δ -3.7 (s), 2.2 (s), 18.5 (s), 71.0 (q, 2 JCF ) 31.5 Hz), 128.2 (q, JCF ) 283. 5 Hz); IR (neat) 2961, 1148, 833 cm -1 ; MS (CI with NH3) m/z 259 (M + 1, 2), 239 (M -HF, 3), 166 (8), 164 (12), 90 (100).…”

Section: Experimental Section 10mentioning

confidence: 99%

“…On the other hand, regioselective cascade cyclization of polyenes was carried out taking advantage of the carbocation stabilizing effect of α-fluorine . The fluorinated monoterpene analogues synthesized so far were substituted on C-2 or on the methyl group bonded to C-3 2a,3b,, or C-7 2c…”

Section: Introductionmentioning

confidence: 99%

Acetyltrimethylsilane, Trifluoromethyltrimethylsilane, and Prenyl Esters: A Three-Component System for the Synthesis of gem-Difluoroanalogues of Monoterpenes

2001

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The preparation of 3,3-difluoro-6-methylhept-5-en-2-one 1, a key intermediate for the synthesis of 4,4-difluoroterpenes, and applications in linalool and geraniol series are described. The process involves 1,1-difluoro-2-trimethylsilyoxypropene, an enol silyl ether prepared from acetyltrimethylsilane and trifluoromethyltrimethylsilane, and its reaction in situ with prenyl benzoate, under catalysis by trimethylsilyl trifluoromethanesulfonate. Optimized conditions leading to either the desired enol silyl ether or the unprecedented methyl(trifluoromethyl)trimethylsilyl carbinol 4 have been achieved. The prenylation of the enol silyl ether gives a 9/1 mixture of regioisomers, in favor of the expected ketone 1. Treatment of 1 with vinylmagnesium bromide leads to (+/-)-4,4-difluorolinalool 7. Reaction with the lithium enolate of ethyl diethylphosphonoacetate, and then LAH reduction, converts 1 to 4,4-difluorogeraniol 11, with complete stereoselectivity.

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“…Therewith occurred a terminal extension of the chain, and the skeleton of the C 7 -C 16 fragment of epothilones was formed. Note that the use of Me 3 SiI for enolsylilation of ketone VII [12,13] gave less pure mixture of ethers VIII (Scheme 1). To carry out a regioselective oxidation of methyl ketone VII at the or c IV CH 2 group adjacent to the carbonyl we first by treating with N,N-(bistrimethylsilyl)acetamide obtained a mixture of enol ethers (VIII, 85%) (similar procedure see.…”

mentioning

confidence: 99%

“…13 and 75.47 ΜHz ( 13 C) from solutions in CDCl 3 , internal reference TMS. IR spectra were recorded on spectrophotometers UR-20 and Specord M-80 (from thin films and mulls in mineral oil).…”

mentioning

confidence: 99%

Chemically Rational Approach to the Synthesis of Precursors of the “Prenyl” Fragment in Epothilones

et al. 2005

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An important stage in the synthesis of the antineoplastic agent epothilone D (I) possessing taxol-like activity is a stereoselective building of block-synthons with 12,13-Z-trisubstituted double bond [1][2][3]. In our approach to compound I [4] this problem was solved by the use of α,ω-bifunctional Z-olefins II and III with a desired stereochemistry readily available by ozonolysis cleavage of cis-1,5-dimethylcyclooctadiene (IV) [5][6][7].First by chemo-and stereoselective olefination of ketoaldehyde II with phosphorane V [8] we obtained ester VI [with Z-isomer content not exceeding 3-4% ( 1 H NMR data)]. Therewith occurred a terminal extension of the chain, and the skeleton of the C 7 -C 16 fragment of epothilones was formed. Further introduction of C 15 -hydroxy function of epothilones in the synthons was demonstrated by an example of compound VII. To carry out a regioselective oxidation of methyl ketone VII at the S N O O O OH 12 7 6 1 16 17 OH O X 12 16

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Synthesis of Fluoromonoterpenoids as potential suicide substrates for plant cells

Cited by 10 publications

References 25 publications

On the isolation of neat allylic fluorides

On the isolation of neat allylic fluorides

Acetyltrimethylsilane, Trifluoromethyltrimethylsilane, and Prenyl Esters: A Three-Component System for the Synthesis of gem-Difluoroanalogues of Monoterpenes

Chemically Rational Approach to the Synthesis of Precursors of the “Prenyl” Fragment in Epothilones

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