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Gold‐Catalyzed Tandem Hydroamination/Formal Aza‐Diels–Alder Reaction of Homopropargyl Amino Esters: A Combined Computational and Experimental Mechanistic Study
Author(s) -
Miró Javier,
SánchezRoselló María,
González Javier,
del Pozo Carlos,
Fustero Santos
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201406224
Subject(s) - hydroamination , stereocenter , tandem , chemistry , catalysis , rationalization (economics) , combinatorial chemistry , amino esters , organic chemistry , enantioselective synthesis , materials science , philosophy , epistemology , composite material
A tandem gold‐catalyzed hydroamination/formal aza‐Diels–Alder reaction is described. This process, which employs quaternary homopropargyl amino ester substrates, leads to the formation of an intrincate tetracyclic framework and involves the generation of four bonds and five stereocenters in a highly diastereoselective manner. Theoretical calculations have allowed us to propose a suitable mechanistic rationalization for the tandem protocol. Additionally, by studying the influence of the ligands on the rate of the gold‐catalyzed reactions, it was possible to establish optimum conditions in which to perform the process with a variety of substituents on the amino ester substrates. Notably, the asymmetric version of the tandem reaction was also evaluated.