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Sequential Intramolecular Diels–Alder Reaction of 3‐Heteroaryl‐2‐propenylamides of Ethenetricarboxylate
Author(s) -
Sugiura Hirotaka,
Yamazaki Shoko,
Ogawa Akiya
Publication year - 2019
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.3665
Subject(s) - chemistry , pyrrolidine , stereoselectivity , amide , chemoselectivity , cycloaddition , intramolecular force , amine gas treating , medicinal chemistry , organic chemistry , stereochemistry , catalysis
The reaction of 1,1,2‐ethenetricarboxylic acid 1,1‐diethyl ester with E ‐3‐(2‐furyl)‐2‐propenylamines under the amide condensation conditions (EDCI/HOBt/Et 3 N) on heating at 80–110°C afforded cis ‐fused tricyclic compounds, furo[ 2,3‐f ]isoindoles as major product. On the other hand, the reaction with E ‐3‐(3‐furyl)‐2‐propenylamines afforded trans ‐fused tricyclic compounds predominantly. The formation of amide/[4 + 2] cycloaddition/hydrogen‐shift reactions proceed sequentially. The observed stereoselectivity of the fused rings has been investigated by the density functional theory calculations. The reaction of 1,1,2‐ethenetricarboxylic acid 1,1‐diethyl ester with 3‐(3‐pyridinyl)‐2‐propen‐1‐amine under the amide condensation conditions afforded HOBt‐incorporated 3,4‐ trans ‐pyrrolidine selectively. The chemoselectivity and stereoselectivity of the reactions with (3‐heteroaryl)‐2‐propen‐1‐amines depend on the nature of heteroarenes.