Chirality probe approach to reactive intermediates : Primary vinyl cation and cycloalkyne
スポンサーリンク
概要
- 論文の詳細を見る
Molecular chirality of 4-methylcyclohexylidenemethyl iodonium salt is used to probe the chirality of intermediate state of the reaction. A possible achiral intermediate, primary vinyl cation is excluded for the reactions of the iodonium salt under any reaction conditions employed, while achiral 5-methyl-cycloheptyne, formed via rearranged cation, is involved in the reaction with sulfonate. The reaction is extended to generation of some small ring cycloalkynes. Vinylic SN2 mechanisms are also proposed.
- 日本学士院の論文
著者
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Okuyama Tadashi
Graduate School Of Material Sci. Himeji Inst. Of Technol. Univ. Of Hyogo Kohto Kamigori Hyogo 678-12
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Fujita Morifumi
Graduate School Of Material Science Himeji Institute Of Technology University Of Hyogo
関連論文
- Reactions of 2,2-Dialkylvinyl Iodonium Salt with Halide Ions
- Solvolysis of 2, 2-Dialkylvinyl Iodonium Salt : Alkyl Participation and Possibility of a Primary Vinylic Cation Intermediate
- Solvolysis of β,β-Dialkylvinyliodonium Salt : Primary Vinyl Cation Intermediate and Alkyl Participation
- Vinylic S_N2 Reaction of 1-Decenyliodonium Salt with Halide Ions
- Ligand Coupling Mechanism of Nucleophilic Vinylic Substitution of Iodonium Salts with Hypervalent 10-I-3 and 12-I-4 Intermediates
- Preparation of Methoxy-Substituted Optically Active 7-Alkoxycarbonylcycloheptatrienes and Their Acid-Promoted Rearrangements
- Perhydroxylation of Chiral Cycloheptatriene Ring through Stepwise Oxidation under Regio- and Stereocontrol
- Regioselective Formation of Optically Active Cycloheptatrienes by Chiral Tethered Buchner Reaction
- Novel Acid-Catalyzed Rearrangement of Alkoxycarbonylcycloheptatriene Assisted by Alkoxy Substitution
- Carbenoid Addition to Phenols to Give Cycloheptatrienols. Stereochemical Regulation and Ligand-dependent Switching of Chemoselectivity
- Stereoselective Intramolecular O-H Insertion of Rhodium Carbenoid Controlled by the 2,4-Pentanediol Tether
- Generation of Cycloheptyne during the Solvolysis of Cyclohexylidenemethyliodonium Salt in the Presence of Base
- Michael Addition of Cyanide to Cyclohex-1-enyliodonium Salts
- Cyclohexynes. Generation from Iodonium Salts and Regioselective Reaction with Nucleophile
- Solvolysis of Optically Active 4-Methylcyclohexylidenemethyl Triflate: Evidence against a Primary Vinyl Cation as an Intermediate
- Regioselectivity in Nucleophilic Addition of Siloxyalkenes to an Alkylideneallyl Cation
- Chirality probe approach to reactive intermediates : Primary vinyl cation and cycloalkyne
- Asymmetric Synthesis of gem-Dimethylcyclopropane-fused Compounds through Chemo-, Regio-, and Stereoselective Cyclopropanation and Stereospecific Rearrangement
- Temperature-Independent Stereoselectivity in Intramolecular Cycloaddition of Ketene Generated from Diazoester in Solution and in Vapor Phase : How Entropy Term Governs the Selectivity