Au(III) complexes with tetradentate-cyclam-based ligands

• Ann Christin Reiersølmoen,
• Thomas N. Solvi and
• Anne Fiksdahl

Beilstein J. Org. Chem. 2021, 17, 186–192, doi:10.3762/bjoc.17.18

• -membered chelate rings. The testing of the catalytic ability of the cyclam-based N,N,N,N-Au(III) complexes demonstrated high catalytic activity of some complexes in selected test reactions (full conversion in 1–24 h, 62–97% product yields). Keywords: Au(III); carboalkoxylation; coordination studies

• , due to sample decomposition. Attempts to obtain crystals for X-ray analysis by slow diffusion of n-pentane into a DCM solution of the complexes were unsuccessful. Catalytic activity For evaluation of the catalytic ability of the new Au(III) complexes, alkyne carboalkoxylation [47][48] and

• activity was observed for cyclam–gold complex 6a-Au(III) versus the open cyclam analogues 5a-Au(III). Complex 5a-Au(III) afforded a full conversion in the alkyne carboalkoxylation in 5.5 hours, compared to in 24 hours for complex 6a-Au(III) (Table 1, entries 1 and 2). The same trend was observed for Au(III

Silver and gold-catalyzed multicomponent reactions

• Giorgio Abbiati and
• Elisabetta Rossi

Beilstein J. Org. Chem. 2014, 10, 481–513, doi:10.3762/bjoc.10.46

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

• enabled the use of simple dimethyl acetals 6 in the carboalkoxylation of alkenes (Scheme 4) [32]. A 1:2 mixture of [picAuCl2] (7) and AgNTf2 efficiently catalyzed the double functionalization of aryl alkenes 4 in good yields and mild conditions. Dialkyl substituted olefins afforded the product only in

• hydroamination intermediate affording tricyclic 3-benzazepines 129 (Scheme 32c). In the same field, Zhang reported the carboamination, carboalkoxylation and carbolactonization of terminal alkenes with arylboronic acids. Under best conditions, oxidative gold catalysis provided expedient access to various

• )]-catalyzed addition of aliphatic alcohols to alkenes. [Au(III)]-catalyzed carboalkoxylation of alkenes with dimethyl acetals 6. Isolation and reactivity of alkyl gold intermediates in the intramolecular hydroamination of alkenes. [Au(I)]-catalyzed intermolecular hydroamination of dienes. Intramolecular [Au(I

Gold-catalyzed intermolecular coupling of sulfonylacetylene with allyl ethers: [3,3]- and [1,3]-rearrangements

• Jungho Jun,
• Hyu-Suk Yeom,
• Jun-Hyun An and
• Seunghoon Shin

Beilstein J. Org. Chem. 2013, 9, 1724–1729, doi:10.3762/bjoc.9.198

• polarization of alkynes both by a gold catalyst and a sulfonyl substituent resulted in an efficient intermolecular tandem carboalkoxylation. Reactions of linear allyl ethers are consistent with the [3,3]-sigmatropic rearrangement mechanism, while those of branched allyl ethers provided [3,3]- and [1,3

• -substituted alkynes underwent an efficient intermolecular carboalkoxylation with allyl ethers via a tandem conjugate addition and a [3,3]-sigmatropic rearrangement [10][11][12]. Preliminary results in the above studies [5][9] have demonstrated that a polarizing effect of the sulfonyl substituent on the alkyne

• + 2] cycloaddition [4][5] where JohnPhos ligand showed the best performance, the optimal ligand for the current carboalkoxylation was different. While the role of electron density of the ligand was less obvious, the steric bulk on the ligand clearly seemed to retard the reaction and a less bulky PPh3

Recent advances in the gold-catalyzed additions to C–C multiple bonds

• He Huang,
• Yu Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2011, 7, 897–936, doi:10.3762/bjoc.7.103

• conversion of C(sp3)–Au bonds into C(sp3)–C(sp2) bonds is an ongoing challenge. In 2010, Zhang’s group reported the first example in an intermolecular oxidative cross-coupling manner [167]. In their pioneering work, carboamination, carboalkoxylation and carbolactonization of terminal alkenes 341 was achieved

Synthesis of the Benzo- fused Indolizidine Alkaloid Mimics

• Daniel L. Comins and
• Kazuhiro Higuchi

Beilstein J. Org. Chem. 2007, 3, No. 42, doi:10.1186/1860-5397-3-42

• -dihydropyridones via palladium mediated cross-coupling and carboalkoxylation. [23] Initially, non-reductive Heck cyclization of 1l [24] was carried out in the presence of Pd(OAc)2 and AgNO3 in CH3CN. [22] Treatment of the product 11 with ICl in CH2Cl2 at 0°C gave the iodinated dihydropyridone 12 in 86% yield

• . Palladium-catalyzed carboalkoxylation reaction of 12 gave the α-methoxycarbonyl dihydropyridone 13 in 82% yield. The addition and modification of functional groups on 8a were investigated (Scheme 4). The protection of the C-4 carbonyl of 8a as a ketal followed by Vilsmeier-Haack formylation [25] furnished