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Gold(I)‐Catalyzed Conia‐ene Cyclization of Internal ϵ ‐Acetylenic β‐Ketoesters under High Pressure.
Author(s) -
Chaładaj Wojciech,
Kołodziejczyk Agata,
Domański Sylwester
Publication year - 2017
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201701388
Subject(s) - moiety , alkyne , steric effects , chemistry , reactivity (psychology) , catalysis , ene reaction , high pressure , medicinal chemistry , stereochemistry , organic chemistry , thermodynamics , pathology , medicine , physics , alternative medicine
The influence of pressure on the gold(I)‐catalyzed Conia‐ene cyclization of ϵ ‐acetylenic‐β‐ketoesters bearing an internal alkyne moiety was investigated for the first time. The reaction catalyzed by commercially available PPh 3 AuNTf 2 complex, which is sluggish at ambient pressure owing to steric reasons, proceeds smoothly under high‐pressure conditions (6 kbar). Mechanistic aspects of the reaction proceeding via 5 ‐ exo‐dig and 6 ‐ endo‐dig cyclization pathways were also studied employing DFT methods. Differences in the reactivity of substrates containing terminal and internal alkynes is discussed.