Palladium-catalyzed three-component radical-polar crossover carboamination of 1,3-dienes or allenes with diazo esters and amines

• Geng-Xin Liu,
• Xiao-Ting Jie,
• Ge-Jun Niu,
• Li-Sheng Yang,
• Xing-Lin Li,
• Jian Luo and
• Wen-Hao Hu

Beilstein J. Org. Chem. 2024, 20, 661–671, doi:10.3762/bjoc.20.59

• -light-mediated palladium-catalyzed three-component radical-polar crossover carboamination of 1,3-dienes or allenes with diazo esters and amines, affording unsaturated γ- and ε-amino acid derivatives with diverse structures. In this methodology, the diazo compound readily transforms into a hybrid α-ester

• multicomponent reaction protocol. Keywords: carboamination; diazo chemistry; palladium catalysis; radical-polar crossover; three-component reaction; Introduction Since the discovery of the existence of non-canonical amino acids (AAs) in organisms, such structural motifs have attracted considerable attention

• be difficult to achieve using either radical or polar chemistry alone. In recent years, Gevorgyan, Glorius, Huang and their co-workers reported elegant examples of the carboamination of 1,3-dienes with unactivated alkyl halides and amines under photoinduced palladium catalysis via a radical-polar

Transition-metal-catalyzed domino reactions of strained bicyclic alkenes

• Austin Pounder,
• Eric Neufeld,
• Peter Myler and
• William Tam

Beilstein J. Org. Chem. 2023, 19, 487–540, doi:10.3762/bjoc.19.38

• reaction to afford the naphthalene product 88a. Inspired by Zhao’s seminal report on the racemic carboamination of bicyclic alkenes [53], the Cramer laboratory studied the Co-catalyzed enantioselective carboamination of bicyclic alkenes 1 via C–H functionalization in 2021 (Scheme 17) [54]. The authors

Iron-catalyzed domino coupling reactions of π-systems

• Austin Pounder and
• William Tam

Beilstein J. Org. Chem. 2021, 17, 2848–2893, doi:10.3762/bjoc.17.196

• rate-determining step of this transformation, as well as free radicals being involved in the reaction mechanism. In 2017, Luo and Li described a three-component Ag-mediated Fe-catalyzed 1,2-carboamination of alkenes 82 using alkyl nitriles 76 and amines 105 for the synthesis of γ-amino alkyl nitriles

• , the reactivity and applicability outperformed the racemic variant. Application of this methodology was applied towards the total synthesis of maraviroc, an anti-HIV drug, which was synthesized in 5 steps starting from styrene (115a) and CBr4 (20a). Carboamination In 2017, the Bao group investigated

• the carboamination of activated alkenes 115 with alkyl diacyl peroxides 163 and acetonitrile (Scheme 34) [136]. Their efficient protocol featured a broad substrate scope, including diversely functionalized styrene derivatives, various alkyl diacyl peroxides, and a few different nitrile solvents which

Visible-light-mediated copper photocatalysis for organic syntheses

• Yajing Zhang,
• Qian Wang,
• Zongsheng Yan,
• Donglai Ma and
• Yuguang Zheng

Beilstein J. Org. Chem. 2021, 17, 2520–2542, doi:10.3762/bjoc.17.169

• radical reacts with the olefin generating a new alkyl radical, which is trapped by CuII/binap/SCF3 to provide the coupling product (Scheme 10). In 2019, Zhang and co-workers [58] reported the photoinduced copper-catalyzed carboamination of alkenes that involved organic halides 16, alkenes, and amines 17

Insertion of [1.1.1]propellane into aromatic disulfides

• Robin M. Bär,
• Gregor Heinrich,
• Martin Nieger,
• Olaf Fuhr and
• Stefan Bräse

Beilstein J. Org. Chem. 2019, 15, 1172–1180, doi:10.3762/bjoc.15.114

• carboamination of 1. This reaction provides access to internal BCPs next to amines [22]. The reaction of 1 with thiophenol has been known since 1985 and, given the high yield, used to determine the concentration of propellane solutions [23]. Our group investigated this reaction further and proved the generality

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

• 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

• . 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

Organocatalytic cascade aza-Michael/hemiacetal reaction between disubstituted hydrazines and α,β-unsaturated aldehydes: Highly diastereo- and enantioselective synthesis of pyrazolidine derivatives

• Zhi-Cong Geng,
• Jian Chen,
• Ning Li,
• Xiao-Fei Huang,
• Yong Zhang,
• Ya-Wen Zhang and
• Xing-Wang Wang

Beilstein J. Org. Chem. 2012, 8, 1710–1720, doi:10.3762/bjoc.8.195

• dipoles. Recently, the Ma group and Toste et al. have reported efficient methods for the synthesis of pyrazolidine derivatives by metal-catalyzed aminations of allenes [28][29][30][31][32]. Meanwhile, Lewis acid catalyzed carboamination reactions have also been reported as efficient methods for the

Amines as key building blocks in Pd-assisted multicomponent processes

• Didier Bouyssi,
• Nuno Monteiro and
• Geneviève Balme

Beilstein J. Org. Chem. 2011, 7, 1387–1406, doi:10.3762/bjoc.7.163

• reaction, two different aryl bromides are sequentially added to the primary aliphatic amine in the presence of a palladium(0) catalyst. The first selective, Pd-catalyzed mono-N-arylation leading to the corresponding γ-(N-arylamino)alkenes 69 is followed by a carboamination reaction, developed by the same

• followed by reductive elimination furnishes N-aryl-2-benzylpyrrolidine derivatives 71. In this process, both reactions are catalyzed by zerovalent palladium and the choice of the phosphine ligand for the N-arylation of amines and the carboamination reactions is of great significance and an in situ

• -alkynylindoles through a Pd-catalyzed Sonogashira/double C–N coupling reaction. Synthesis of indoles through a Pd-catalyzed sequential alkenyl amination/C-arylation/N-arylation. Synthesis of N-aryl-2-benzylpyrrolidines through a sequential N-arylation/carboamination reaction. Synthesis of phenothiazine

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