Synthesis of 7-alkyl-cycloheptatrienes from allylic silanes and tropylium tetrafluoroborate

Picotin, G.; Miginiac, Ph.

doi:10.1016/s0040-4039(00)82219-4

Cited by 11 publications

(5 citation statements)

References 13 publications

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“…The analogous reaction with allyltributylstannane ( 14c ) afforded the complex 15b (Scheme ). The corresponding reaction of the noncoordinated tropylium ion 1 with (2-methylallyl)trimethylsilane ( 14a ) has already been reported . As shown in Scheme , tropylium triflate ( 1-OTf ) reacts with α-(trimethylsiloxy)styrene ( 17 ) to give the ketone 18 , which had previously been obtained by treatment of tropylium tetrafluoroborate ( 1-BF 4 ) with acetophenone .…”

Section: Resultsmentioning

confidence: 94%

“…The corresponding reaction of the noncoordinated tropylium ion 1 with (2-methylallyl)trimethylsilane (14a) has already been reported. 21 As shown in Scheme 3, tropylium triflate (1-OTf) reacts with R-(trimethylsiloxy)styrene (17) to give the ketone 18, which had previously been obtained by treatment of tropylium tetrafluoroborate (1-BF 4 ) with acetophenone. 22 Hydride transfer from triphenylstannane (19) to the tropylium ion (1) gave cycloheptatriene (2) (Scheme 3), in analogy to the reported reaction of 1 with dimethylphenylsilane (20).…”

Section: Resultsmentioning

confidence: 99%

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Comparison of the Electrophilicities of the Free and the (Tricarbonyl)iron-Coordinated Tropylium Ion

et al. 1999

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The kinetics of the reactions of the tropylium ion (1) and the (tricarbonyl)iron-coordinated tropylium ion (6) with allylsilanes, allylstannanes, and other uncharged nucleophiles were studied photometrically and conductometrically. The second-order rate constants were independent of the counterions, indicating rate-determining carbon−carbon bond formation. The electrophilicity parameters of the (tricarbonyl)iron complexes of the tropylium ion E(6) = −3.81 ± 0.24 and of the dihydrotropylium ion E(22) = −9.88 indicate that the former is 105−106 times more reactive toward nucleophiles. Comparison with the electrophilicity parameter of the free tropylium ion E(1) = −4.62 ± 0.57 shows that coordination by Fe(CO)3 affects its electrophilic reactivity only slightly. Density-functional calculations are used to rationalize the relative reactivities in terms of thermodynamic effects and frontier orbital interactions. On the basis of the linear free enthalpy relationship log k = s(E + N) one can predict that the free and the Fe(CO)3-coordinated tropylium ion react with nucleophiles (N > −1) at room temperature.

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Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

Comparison of the Electrophilicities of the Free and the (Tricarbonyl)iron-Coordinated Tropylium Ion

et al. 1999

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“…The chemistry of these species has obtained high attention by many researches [2]. Moreover, tropylium tetrafluoroborate is considered as one of the most interesting compounds in several fields [3].…”

Section: Issn: 0067-2904mentioning

confidence: 99%

“…Tropylium salts are also utilized as typical reagents in the synthesis of N-tropylanilines [6]. This tropylium salt can be easily obtained by hydride elimination from cycloheptatriene, either by triphenylcarbenium tetrafluoroborate [7] or by phosphorus (V) chloride and tetrafluoroboric acid solution [8].…”

Section: Issn: 0067-2904mentioning

confidence: 99%

Synthesis and Characterization of Some New Tropylidene Derivatives and Studying their Biological Activities

Al-Abbasee

jebur

Shihab

2021

eijs

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“…Therefore, we also investigated the reactions of the corresponding crotyllithium and crotylzinc bromide reagents. Crotyllithium ( 4b ) was prepared according to the literature from crotyl phenyl ether and lithium. , CrotylZnBr·LiCl ( 4c ) was obtained according to the procedure of Knochel et al from trans -crotyl bromide and Zn in the presence of LiCl. This method allows the preparation of substituted allylzinc reagents almost without homocoupling. , …”

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confidence: 99%

Application of Allylzinc Reagents as Nucleophiles in Matteson Homologations

Andler

Kazmaier

2021

Org. Lett.

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Allylzinc reagents are versatile nucleophiles that can be used in Matteson homologations. The linear substitution products are formed almost exclusively, and excellent E selectivities are observed in reactions of reagents with sterically demanding or aryl substituents on the double bond. The allylated boronic esters obtained can be converted into trifluoroborates or subjected to further homologations. Ozonolysis of the double bond provides aldehydes or ketones, and therefore, allylzinc reagents are useful acetaldehyde or ketone enolate equivalents.

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Synthesis of 7-alkyl-cycloheptatrienes from allylic silanes and tropylium tetrafluoroborate

Cited by 11 publications

References 13 publications

Comparison of the Electrophilicities of the Free and the (Tricarbonyl)iron-Coordinated Tropylium Ion

Comparison of the Electrophilicities of the Free and the (Tricarbonyl)iron-Coordinated Tropylium Ion

Synthesis and Characterization of Some New Tropylidene Derivatives and Studying their Biological Activities

Application of Allylzinc Reagents as Nucleophiles in Matteson Homologations

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