title: Stereoselective gold(I) domino catalysis of allylic isomerization and olefin cyclopropanation: mechanistic studies.
abstract: Gold(I) catalysis of olefin activation is still a rare feature in the repertoire of that metal. Mechanistic studies on the gold(I)-catalyzed cyclopropanation of allyl-substituted sulfonium ylides, including kinetic analysis as well as detailed computational studies, reveal that the reaction proceeds through activation of the alkene moiety. Furthermore, a novel competitive allylic isomerization pathway that interconverts "linear" and "branched" allylic isomers is uncovered. The subtle interplay of cyclopropanation and olefin isomerization results in an intriguing domino process where two independent catalytic transformations combine with near-perfect regio- and stereoselectivities.
authors.affiliation: †Faculty of Chemistry, Institute of Organic Chemistry, University of Vienna, Währinger Strasse 38, 1090 Vienna, Austria.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Klimczyk
authors.affiliation: ‡State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fujian 350002, China.
authors.forename: Xueliang
authors.initials: X
authors.lastname: Huang
authors.affiliation: †Faculty of Chemistry, Institute of Organic Chemistry, University of Vienna, Währinger Strasse 38, 1090 Vienna, Austria.
authors.forename: Hanspeter
authors.initials: H
authors.lastname: Kählig
authors.affiliation: §Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais 1, 1049-001 Lisbon, Portugal.
authors.forename: Luís F
authors.initials: LF
authors.lastname: Veiros
authors.affiliation: †Faculty of Chemistry, Institute of Organic Chemistry, University of Vienna, Währinger Strasse 38, 1090 Vienna, Austria.
authors.forename: Nuno
authors.initials: N
authors.lastname: Maulide