Although literature abounds with examples of formation of perhaloalkanes by photo-lytic or Lewis-acid induced halogen exchange reactions involving radical or carbocationintermediates,the procedures are seldom applicab...Although literature abounds with examples of formation of perhaloalkanes by photo-lytic or Lewis-acid induced halogen exchange reactions involving radical or carbocationintermediates,the procedures are seldom applicable to the preparation of perhaloalkanes ingood yields under mild conditions.Recently,we have reported the spontaneous reactionsof some perhalofluoroalkanes with various types of nucleophiles.All these reactions areinitiated by the halophilic attack of nucleophiles on C—Br or C—Cl bonds,followed byanionic chain steps involving carbanion as well as olefin intermediates.Notably,the latter areformed after the β-elimination of a good leaving group from the former.On the other hand,it is well known that halogenated carbanions can effectively make halophilic attacks on theC—X bonds of other halogenated substrates,e.g.,in the“halogen dance”of Bunnett.There-展开更多
a-Oxo ketene dithioacetals 2 via 1,2-nucleophilie addition by methallyl magnesius chloride afforded corresponding alcohols (3). Treated with water or methanol and catalyzed by Lewis acid, the alcohols 3 were converted...a-Oxo ketene dithioacetals 2 via 1,2-nucleophilie addition by methallyl magnesius chloride afforded corresponding alcohols (3). Treated with water or methanol and catalyzed by Lewis acid, the alcohols 3 were converted regiospecifical ly to substituted phenols 5' or related phenol methyl ethers 5 respectively. This reaction is a novel approach to the synthesis of phenols and their derivatives starting from non-aromatic precursors.展开更多
Perfluoroalkyl chloride can be converted into hydroperfluoroalkane with zinc powder in the presence of nickel dichloride.A single electron transfer mechanism is proposed.
基金the National Natural Science Foundation of China.
文摘Although literature abounds with examples of formation of perhaloalkanes by photo-lytic or Lewis-acid induced halogen exchange reactions involving radical or carbocationintermediates,the procedures are seldom applicable to the preparation of perhaloalkanes ingood yields under mild conditions.Recently,we have reported the spontaneous reactionsof some perhalofluoroalkanes with various types of nucleophiles.All these reactions areinitiated by the halophilic attack of nucleophiles on C—Br or C—Cl bonds,followed byanionic chain steps involving carbanion as well as olefin intermediates.Notably,the latter areformed after the β-elimination of a good leaving group from the former.On the other hand,it is well known that halogenated carbanions can effectively make halophilic attacks on theC—X bonds of other halogenated substrates,e.g.,in the“halogen dance”of Bunnett.There-
文摘a-Oxo ketene dithioacetals 2 via 1,2-nucleophilie addition by methallyl magnesius chloride afforded corresponding alcohols (3). Treated with water or methanol and catalyzed by Lewis acid, the alcohols 3 were converted regiospecifical ly to substituted phenols 5' or related phenol methyl ethers 5 respectively. This reaction is a novel approach to the synthesis of phenols and their derivatives starting from non-aromatic precursors.
基金This work was supported by the National Natural Science Foundation of China.
文摘Perfluoroalkyl chloride can be converted into hydroperfluoroalkane with zinc powder in the presence of nickel dichloride.A single electron transfer mechanism is proposed.
