13609-59-1Relevant articles and documents
Photosolvolysis of optically active 4-methyl-cyclohexylidenemethyl(aryl)iodonium tetrafluoroborate
Fujita, Morifumi,Furutani, Machiko,Okuyama, Tadashi
, p. 8579 - 8581 (2002)
The title reaction gives largely racemized 4-methylcycloheptanone, but the enantiomeric product in slight excess has a different form depending on the leaving group, ArI, of the iodonium salt. The results indicate that the photosolvolysis does not proceed via a completely achiral state.
Solvolysis of optically active 4-methylcyclohexylidenemethyl triflate: Evidence against a primary vinyl cation as an intermediate
Fujita, Morifumi,Yamamoto, Akiyo,Sugimura, Takashi,Okuyama, Tadashi
, p. 806 - 807 (2001)
Solvolysis of (R)-4-methylcyclohexylidenemethyl triflate in aqueous methanol at 140 °C gave stereospecifically (R)-4-methylcycloheptanone to definitively rule out intermediate formation of the achiral primary vinyl cation. The rearrangement must occur via concerted σ-bond participation.
Solvolysis of 4-methylcyclohexylidenemethyliodonium salt: Chirality probe approach to a primary vinyl cation intermediate
Fujita, Morifumi,Sakanishi, Yuichi,Nishii, Masayoshi,Yamataka, Hiroshi,Okuyama, Tadashi
, p. 8130 - 8137 (2007/10/03)
Optically active 4-methylcyclohexylidenemethyl(aryl)iodonium tetrafiuoroborate (1·BF4-) was prepared and its solvolysis was carried out at 60 °C in various solvents. The main product is optically active 4-methylcycloheptanone (or its enol derivative) in unbuffered solvents, accompanied by the iodoarene. The rearranged product always maintains the optical purity of the starting 1. Its stereochemistry conforms to a mechanism involving the rearrangement via the σ-bond participation in departure of the nucleofuge, followed by trapping of the resulting chiral 5-methylcyclohept-1-enyl cation with a nucleophilic solvent. That is, the achiral, primary vinyl cation is not involved during the reaction. The unrearranged substitution product is also obtained in a minor fraction in unbuffered methanol, ethanol, and acetic acid, but not in trifluoroethanol or hexafluoro-2-propanol: the methoxy product from methanolysis is largely racemized, but the acetolysis product is obtained mainly via retention of configuration. Reactions of 1 with bromide, acetate, and trifluoroacetate in chloroform give unrearranged substitution products in different degrees of inversion. These unrearranged products are concluded to be formed via the direct nucleophilic substitutions. Added bases such as sodium acetate in methanol lead to the unrearranged methoxy products of complete racemization, which is ascribed to the α elimination (to give an alkylidene-carbene) followed by the solvent insertion.