20657-21-0Relevant articles and documents
Michael addition-elimination mechanism for nucleophilic substitution reaction of cycloalkenyl iodonium salts and selectivity of 1,2-hydrogen shift in cycloalkylidene intermediate
Fujita, Morifumi,Wan, Hyeok Kim,Fujiwara, Koji,Okuyama, Tadashi
, p. 480 - 488 (2007/10/03)
(Chemical Equation Presented) Reactions of cyclohexenyl and cyclopentenyl iodonium salts with cyanide ion in chloroform give cyanide substitution products of allylic and vinylic forms. Deuterium-labeling experiments show that the allylic product is formed via the Michael addition of cyanide to the vinylic iodonium salt, followed by elimination of the iodonio group and 1,2-hydrogen shift in the 2-cyanocycloalkylidene intermediate. The hydrogen shift preferentially occurs from the methylene rather than the methine β-position of the carbene, and the selectivity is rationalized by the DFT calculations. The Michael reaction was also observed in the reaction of cyclopentenyliodonium salt with acetate ion in chloroform. The vinylic substitution products are ascribed to the ligand-coupling (via λ3-iodane) and elimination-addition (via cyclohexyne) pathways.
ACYLOXYLATION OF CYCLOPENTADIENE IN THE PRESENCE OF PALLADIUM COMPLEXES
Vekki, A. V.,Trushova, N. V.
, p. 394 - 396 (2007/10/02)
Cyclopentadiene reacts with PdCl4-2 in acetic acid to form a binuclear bridged complex, which probably has an asymmetric sandwich structure with one double bond being retained in the ring.The first acetoxy group is introduced almost instantaneously.This is followed by the attack of the second AcO- group or by the decomposition of the complex to form 3-acetoxycyclopentene.With using butyric acid, 3-butyroxycyclopentene is formed with higer selectivity.In the presence of the PdCl4-2-NaNO3-KIO3 system, the reaction becomes catalytic.
PALLADIUM-CATALYZED ALLYLIC OXIDATION OF OLEFINS BY t-BUTYL HYDROPEROXIDE AND TELLURIUM(IV) OXIDE
Uemura, Sakae,Fukuzawa, Shin-ichi,Toshimitsu, Akio,Okano, Masaya
, p. 87 - 90 (2007/10/02)
Treatment of several cyclic olefins, β-pinene, allylbenzene and estragole with palladium(II) salt in acetic acid in the presence of t-butyl hydroperoxide and tellurium(IV) oxide afforded mainly the corresponding allylic acetates.The reaction proceeded catalytically with palladium(II) salt, t-BuOOH working as a reoxidazing agent.
OAc AS A HOMOGENEOUS CATALYST FOR SELECTIVE ENONE FORMATION BY ALLYLIC OXIDATION OF OLEFINS
Uemura, Sakae,Patil, Suresh R.
, p. 4353 - 4356 (2007/10/02)
Treatment of several cyclic olefins and allylbenzene with a catalytic amount of OAc in acetic acid in the presence of t-butyl hydroperoxide affords the corresponding α,β-unsaturated carbonyl compounds(enones) highly selectively via an ionic pathway.
