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The Dichotomy of Gold‐catalyzed Interplay between Cyanamides and Ynamides: Controllable Switch from [2+2+2] to [4+2] Cycloaddition
Author(s) -
Dubovtsev Alexey Yu.,
Shcherbakov Nikolay V.,
Dar'in Dmitry V.,
Kukushkin Vadim Yu.
Publication year - 2020
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.202000434
Subject(s) - cycloaddition , chemistry , regioselectivity , catalysis , pyrimidine , reactivity (psychology) , combinatorial chemistry , reaction conditions , isoquinoline , computational chemistry , medicinal chemistry , stereochemistry , organic chemistry , medicine , alternative medicine , pathology
The gold‐catalyzed interplay between cyanamides and ynamides demonstrates condition‐dependent mechanistic dichotomy. [2+2+2] Cycloaddition proceeds under kinetically controlled conditions to give 2,4,6‐triaminopyrimidines (19 examples, up to 99%). Under thermodynamically controlled conditions, the reactivity switches from [2+2+2]‐ to [4+2] cycloaddition; the latter [4+2] reaction accomplishes 1,3‐diaminoisoquinolines (19 examples, up to 97%). The advantages of both methods include regioselectivity, mild reaction conditions (even for the thermodynamically controlled [4+2] reaction) and the possibility of introducing a variety of dialkyl, diaryl, and heterocyclic amino substituents into the target pyrimidine and isoquinoline cores. The reactions were conducted on gram scales and the versatility of the obtained products was demonstrated by post‐functionalizations.