Methodologies for the synthesis of quaternary carbon centers via hydroalkylation of unactivated olefins: twenty years of advances

• Thiago S. Silva and
• Fernando Coelho

Beilstein J. Org. Chem. 2021, 17, 1565–1590, doi:10.3762/bjoc.17.112

• reported the use of active methylene compounds as suitable nucleophiles in intramolecular hydroalkylation reactions (Scheme 2) [25]. In the presence of PdCl2(CH3CN)2, the hydroalkylation of β-diketones 1 gave only 6-endo-trig cyclization products 2 in moderate to good yields (Scheme 2). The methodology

• nucleophilic attack on the metal-complexed olefin (see Scheme 3, intermediate A). Taking advantage of HCl as an additive (or generated in situ by silyl chloride hydrolysis), Widenhoefer described the intramolecular hydroalkylation of even less reactive alkenyl ketones 4 under Pd(II) catalysis, with minor

• . Cationic gold(I) complexes are also suitable catalysts for olefin functionalization, and their use has become more popular than gold(III) catalysis [39]. In 2007, Che and Zhou reported the olefin intramolecular hydroalkylation of N-alkenyl β-ketoamides 13 using the gold(I)–phosphine complex Au[P(t-Bu)2(o

New developments in gold-catalyzed manipulation of inactivated alkenes

• Michel Chiarucci and
• Marco Bandini

Beilstein J. Org. Chem. 2013, 9, 2586–2614, doi:10.3762/bjoc.9.294

• anti-elimination was invoked to account for the observed experimental outcome (Scheme 29d). A complementary approach for the enantioselective synthesis of 3,4-disubstituted pyrrolidines was recently reported by Bandini and co-workers [72]. Intramolecular hydroalkylation of allylic alcohols with

• . Enantioselective intramolecular hydroalkylation of allylic alcohols with aldehydes catalyzed by 20c and chiral secondary amine. Gold-catalyzed intramolecular diamination of alkenes. Gold-catalyzed aminooxygenation and aminoarylation of alkenes. Gold-catalyzed carboamination, carboalkoxylation and

Efficient gold(I)/silver(I)-cocatalyzed cascade intermolecular N-Michael addition/intramolecular hydroalkylation of unactivated alkenes with α-ketones

• Ya-Ping Xiao,
• Xin-Yuan Liu and
• Chi-Ming Che

Beilstein J. Org. Chem. 2011, 7, 1100–1107, doi:10.3762/bjoc.7.126

• AgClO4 catalyzed intermolecular N-Michael addition and the subsequent gold(I)-catalyzed hydroalkylation is proposed. Keywords: cascade; cocatalyzed; gold(I)-catalyzed; intramolecular hydroalkylation; intermolecular N-Michael addition; pyrrolidine; silver(I)-catalyzed; Introduction Gold complexes are

• cascade intermolecular N-Michael addition/intramolecular hydroalkylation process. A variety of pyrrolidine compounds were conveniently prepared in moderate to excellent yields and with moderate to good diastereoselectivities from the simple starting materials. More recently, we have reported that gold(I

• ) complexes can efficiently catalyze direct intramolecular hydroalkylation of unactivated alkenes with α-ketones, via the exo-trig cyclization, to build a variety of new five- and six-membered rings [24]. However, all of the substrates examined in this gold(I)-catalyzed reaction were prepared and isolated