150668-37-4Relevant articles and documents
Silylium-Ion-Promoted (5+1) Cycloaddition of Aryl-Substituted Vinylcyclopropanes and Hydrosilanes Involving Aryl Migration
Bonetti, Vittorio,He, Tao,Klare, Hendrik F. T.,Oestreich, Martin,Wang, Guoqiang
supporting information, p. 12186 - 12191 (2020/05/22)
A transition-metal-free (5+1) cycloaddition of aryl-substituted vinylcyclopropanes (VCPs) and hydrosilanes to afford silacyclohexanes is reported. Catalytic amounts of the trityl cation initiate the reaction by hydride abstraction from the hydrosilane, and further progress of the reaction is maintained by self-regeneration of the silylium ions. The new reaction involves a [1,2] migration of an aryl group, eventually furnishing 4- rather than 3-aryl-substituted silacyclohexane derivatives as major products. Various control experiments and quantum-chemical calculations support a mechanistic picture where a silylium ion intramolecularly stabilized by a cyclopropane ring can either undergo a kinetically favored concerted [1,2] aryl migration/ring expansion or engage in a cyclopropane-to-cyclopropane rearrangement.
NOVEL TRPV3 MODULATORS
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Paragraph 1606; 1607, (2013/06/04)
Disclosed herein are modulators of TRPV3 of formula (II): wherein G1, X1, X2, X3, X4, X5, G2, Ra, Rb, and u are as defined in the specification. Composition
Precise Control of the Formation of a Covalent and an Ionic Bond in Carbocation-Carbanion Combination Reactions
Takeuchi, Ken'ichi,Kitagawa, Toshikazu,Miyabo, Atsushi,Hori, Hideshi,Komatsu, Koichi
, p. 5802 - 5810 (2007/10/02)
The electronic effect on the selectivity of covalent or ionic bond formation was examined for the reaction of Kuhn's anion 1(1-) (C67H39(1-); tris(7H-dibenzofluorenylidenemethyl)methide ion) and 1-aryl-2,3-dicyclopropylcyclopropenylium ions.The carbocation stability was progressively changed by varying the substituent on the phenyl ring, while the steric effect was kept essentially unchanged.The cations having the p-chlorophenyl (2a(1+)), phenyl (2b(1+)), m-methylphenyl (2c(1+)), or m,m'-dimethylphenyl (2d(1+)) group gave a covalent product, whereas a carbocation-carbanion salt was obtained from the cations having the p-methylphenyl (2e(1+)) or p-methoxyphenyl (2f(1+)) group.The reduction potentials Ered of the cations, as determined by cyclic voltammetry, showed that the formation of the covalent or ionic product is switched by a small difference in stability ( 0.4 kcal/mol) between 2d(1+) and 2e(1+).In chloroform, the salts 1(1-)2e(1+) and 1(1-)2f(1+) were transformed into covalent forms 1-2e and 1-2f, which can exist only in solution.When 1-(2a-d) and 1(1-)2e,f(1+) were dissolved in DMSO, equilibrium between a covalent compound and ions was established.A plot of the free energy of heterolysis ΔG0het for 1-(2a-f) against the Ered of the corresponding cations 2a-f(1+) showed that ΔG0het decreases as the cation is more stabilized.The heterolysis in DMSO was shown to be enhanced by ca. 13 kcal/mol both by the steric congestion in the covalent molecules and the stabilization of the cyclopropenylium ions by solvation.