Open AccessSynthetic Studies on Tricyclic Diterpenoids: Direct Allylic Amination Reaction of Isopimaric Acid Derivatives
Author(s) -
Timoshenko Mariya A.,
Kharitonov Yurii V.,
Shakirov Makhmut M.,
Bagryanskaya Irina Yu.,
Shults Elvira E.
Publication year - 2016
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.201500187
Subject(s) - allylic rearrangement , amination , chemistry , aniline , nucleophile , trifluoromethyl , organic chemistry , hydroamination , carbamate , medicinal chemistry , catalysis , alkyl
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.