Synthetic Studies on Tricyclic Diterpenoids: Direct Allylic Amination Reaction of Isopimaric Acid Derivatives.
A selective synthesis of 7- or 14-nitrogen containing tricyclic diterpenoids was completed according to a strategy in which the key step was the catalyzed direct allylic amination of methyl 14α-hydroxy-15,16-dihydroisopimarate with a wide variety of nitrogenated nucleophiles. It was revealed that the selectivity of the reaction depends on the nature of nucleophile. The catalyzed reaction of the mentioned diterpenoid allylic alcohol with 3-nitroaniline, 3-(trifluoromethyl)aniline, and 4-(trifluoromethyl)aniline yield the subsequent 7α-, 7β- and 14αnitrogen-containing diterpenoids. The reaction with 2-nitroaniline, 4-nitro-2-chloroaniline, 4-methoxy-2-nitroaniline, phenylsulfamide, or tert-butyl carbamate proceeds with the formation of 7α-nitrogen-substituted diterpenoids as the main products.
Laboratory of Medicinal Chemistry Novosibirsk Institute of Organic Chemistry, Siberian Branch Russian Academy of Sciences Lavrentyev Avenue, 9 630090 Novosibirsk Russia; Chemical and Physical Departments Novosibirsk State University Pirogova St. 2 630090 Novosibirsk Russia.
Mariya A
MA
Timoshenko
Laboratory of Medicinal Chemistry Novosibirsk Institute of Organic Chemistry, Siberian Branch Russian Academy of Sciences Lavrentyev Avenue, 9 630090 Novosibirsk Russia; Chemical and Physical Departments Novosibirsk State University Pirogova St. 2 630090 Novosibirsk Russia.
Yurii V
YV
Kharitonov
Laboratory of Medicinal Chemistry Novosibirsk Institute of Organic Chemistry, Siberian Branch Russian Academy of Sciences Lavrentyev Avenue, 9 630090 Novosibirsk Russia.
Makhmut M
MM
Shakirov
Laboratory of Medicinal Chemistry Novosibirsk Institute of Organic Chemistry, Siberian Branch Russian Academy of Sciences Lavrentyev Avenue, 9 630090 Novosibirsk Russia; Chemical and Physical Departments Novosibirsk State University Pirogova St. 2 630090 Novosibirsk Russia.
Irina Yu
IY
Bagryanskaya
Laboratory of Medicinal Chemistry Novosibirsk Institute of Organic Chemistry, Siberian Branch Russian Academy of Sciences Lavrentyev Avenue, 9 630090 Novosibirsk Russia; Chemical and Physical Departments Novosibirsk State University Pirogova St. 2 630090 Novosibirsk Russia.
Elvira E
EE
Shults
allylic amination reaction; diterpenoids; gold catalysis; pimaranes; stereoselectivity