A novel three-component carbon-carbon forming reaction is discovered. Reaction of methyl phenyldiazoacetate with both imine and arylamine in the presence of dirhodium acetate catalyst gives good yields of 1,2-diamines...A novel three-component carbon-carbon forming reaction is discovered. Reaction of methyl phenyldiazoacetate with both imine and arylamine in the presence of dirhodium acetate catalyst gives good yields of 1,2-diamines 5 in competition with N-H insertion to yield 4. While the product ratio is dependent on the electronic features from aryl substitution of the corresponding amine, diastereoselectivity of 5 was consistently high (greater than 10:1 ). Although N-H insertion is competitive, this pathway can be minimized by the use of excess imine. A plausible mechanism revealed that the key intermediate is proposed to be ammonium ylide. This discovery is useful for the preparation of 1,2-diamines with high diastereoselectivity.……展开更多
文摘A novel three-component carbon-carbon forming reaction is discovered. Reaction of methyl phenyldiazoacetate with both imine and arylamine in the presence of dirhodium acetate catalyst gives good yields of 1,2-diamines 5 in competition with N-H insertion to yield 4. While the product ratio is dependent on the electronic features from aryl substitution of the corresponding amine, diastereoselectivity of 5 was consistently high (greater than 10:1 ). Although N-H insertion is competitive, this pathway can be minimized by the use of excess imine. A plausible mechanism revealed that the key intermediate is proposed to be ammonium ylide. This discovery is useful for the preparation of 1,2-diamines with high diastereoselectivity.……
