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α,β‐Unsaturated Gold(I) Carbenes by Tandem Cyclization and 1,5‐Alkoxy Migration of 1,6‐Enynes: Mechanisms and Applications
Author(s) -
Calleja Pilar,
Pablo Óscar,
Ranieri Beatrice,
Gaydou Morgane,
Pitaval Anthony,
Moreno María,
Raducan Mihai,
Echavarren Antonio M.
Publication year - 2016
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.201602347
Subject(s) - propargyl , alkoxy group , chemistry , racemization , alkylation , tandem , formal synthesis , ether , cyclopropanation , medicinal chemistry , stereochemistry , combinatorial chemistry , alkyl , organic chemistry , catalysis , materials science , composite material
1,6‐Enynes bearing OR groups at the propargyl position generate α,β‐unsaturated gold(I)‐carbenes/ gold(I) stabilized allyl cations that can be trapped by alkenes to form cyclopropanes or 1,3‐diketones to give products of α‐alkylation. The best migrating group is p ‐nitrophenyl ether, which leads to the corresponding products without racemization. Thus, an improved formal synthesis of (+)‐schisanwilsonene A has been accomplished. The different competitive reaction pathways have been delineated computationally.