Regioselective Gold-Catalyzed Allylative Ring Opening of 1,4-Epoxy-1,4-dihydronaphthalenes

Abstract

In the presence of a gold catalyst, the ring opening of 1,4-epoxy-1,4-dihydronaphthalenes with allyltrimethylsilane affords allylnaphthalenes in high yield. For unsymmetrical substrates, high regioselectivity is observed in many cases. This reaction might proceed via tricyclic tetrahydrofuran intermediates which are formed stereoselectively.

Gold-catalyzed reaction of oxabicyclic alkenes with electron-deficient terminal alkynes to produce acrylate derivatives

“…Based on the previously established mechanistic model [23,77], we propose the following pathway for the formation of acrylate derivatives 3a and 3i (Scheme 4). In the presence of cationic phosphinogold(I) complex, a cationic intermediate A is formed by a regioselective opening of the oxygen bridge in substrate 1a .…”

“…For example, they are often used to construct substituted tetrahydronaphthalene skeletons in the presence of metal catalysts such as Pd [9–10], Ir [11–15], Rh [16–21] and Cu [22]. However, their reactivity in the presence of gold catalysts has been rarely reported [23]. It is well known that gold catalysts have different catalytic abilities compared with other transition metals [24].…”

Gold-Catalyzed Benzylic Azidation of Phthalans and Isochromans and Subsequent FeCl₃-Catalyzed Nucleophilic Substitutions

“…[9][10][11][12][13] We have continuously investigated the iron [14][15][16][17][18][19][20] -or gold [21][22][23] -catalyzed activation at the benzylic position of various skeletons accompanied by the benzylic C-O bond cleavage. During these investigations, the benzylic position of phthalan (1; n=1) as a benzene fused cyclic ether was found to be directly azidated in the presence of a gold catalyst and trimethylsilylazide (TMSN 3 ) without the C-O bond cleavage to give the 1-azido phthalan (2) (Chart 1).…”

Dual Hard/Soft Gold Catalysis: Intermolecular Friedel–Crafts‐Type α‐Amidoalkylation/Alkyne Hydroarylation Sequences by N‐Acyliminium Ion Chemistry

“…Early literature reports in this area were mainly devoted to Lewis acid activation of carbonyl compounds,3, 4 but recent reports have shown that Au I and Au III salts are also competent catalysts in the mediation of dehydrative couplings of activated π alcohols (and their ether or ester derivatives) with many types of carbo‐ and heteronucleophiles 5. Highly reactive substrates such as doubly π‐activated alcohols, that is, precursors of well‐stabilized cations, have generally been used in intermolecular reactions6a–n whereas gold‐catalyzed intramolecular dehydrative couplings with good neutral nucleophiles (indoles, heteronucleophiles) tolerated less reactive substrates such as simple primary allylic alcohols 6o,p. To broaden the general scope of gold catalysis, it is important to expand the range of substrates and functional groups that can be activated by gold complexes 7 .…”