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

Room-temperature Pd/Ag direct arylation enabled by a radical pathway

• Amy L. Mayhugh and
• Christine K. Luscombe

Beilstein J. Org. Chem. 2020, 16, 384–390, doi:10.3762/bjoc.16.36

• majority of experimental evidence supporting this pathway [22][23][24][25][26]. In this case, C2 selectivity is often observed, theoretically from a C3/C2 Pd migration. A third possible mechanism that has had little experimental evidence but cannot be ruled out, is a Heck-type carbopalladation. This

Synthesis of 1-indanones with a broad range of biological activity

• Marika Turek,
• Dorota Szczęsna,
• Marek Koprowski and
• Piotr Bałczewski

Beilstein J. Org. Chem. 2017, 13, 451–494, doi:10.3762/bjoc.13.48

• 90, it has been proved that this reaction proceeds with participation of Ni-complex 91 isolated in 83% yield which next was converted to 1-indanone 90a via the monomeric complex 92 or its dimer. o-Bromobenzaldehyde 93, in the presence of a palladium catalyst, underwent intermolecular carbopalladation

Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates

• Mohammad Haji

Beilstein J. Org. Chem. 2016, 12, 1269–1301, doi:10.3762/bjoc.12.121

• multicomponent reactions Transition metals, especially Pd and Cu, are well-known catalysts for multicomponent reactions. Carbopalladation reactions of allenes, alkynes and carbon monoxide are very important processes in multicomponent syntheses. Additionally, copper-catalyzed multicomponent reactions such as

Regioselective palladium-catalyzed ring-opening reactions of C1-substituted oxabicyclo[2,2,1]hepta-2,5-diene-2,3-dicarboxylates

• Michael Edmunds,
• Mohammed Abdul Raheem,
• Rebecca Boutin,
• Katrina Tait and
• William Tam

Beilstein J. Org. Chem. 2016, 12, 239–244, doi:10.3762/bjoc.12.25

• . This complex undergoes exo selective coordination with 2, which is likely promoted by the Lewis acid ZnCl2 removing the iodide from 7 allowing it to associate with the oxanorbornadiene. This is quickly followed by carbopalladation onto the exposed olefin to give intermediate 8. There are two possible

Multicomponent reactions in nucleoside chemistry

• Mariola Koszytkowska-Stawińska and
• Włodzimierz Buchowicz

Beilstein J. Org. Chem. 2014, 10, 1706–1732, doi:10.3762/bjoc.10.179

• nucleosides 93 were also prepared by this method. 7. The carbopalladation of dienes A reaction of an aryl halide, an unsaturated alkene (diene, allene), and an amine catalyzed by Pd(0) species, referred to as carbopalladation of dienes, results in the three-component assembly of an unsaturated amine (Scheme

• , 25 °C, 5 d. Bu4N+HSO4−, diethylene glycol, 80 °C, 1–2 h. The three-component carbopalladation of dienes on the example of buta-1,3-diene. Reagents and reaction conditions: i. 5 mol % Pd(dba)2, Bu4NCl, ZnCl2, acetonitrile or DMSO, 80 °C or 100 °C, 1–2 days. Reagents and reaction conditions: i. 2.5 mol

Rational design of cyclopropane-based chiral PHOX ligands for intermolecular asymmetric Heck reaction

• Marina Rubina,
• William M. Sherrill,
• Alexey Yu. Barkov and
• Michael Rubin

Beilstein J. Org. Chem. 2014, 10, 1536–1548, doi:10.3762/bjoc.10.158

• oxidative addition of Pd(0) species 5 into the aryl triflate 2 resulting in the formation of cationic complex 6. The latter can coordinate to either of the prochiral faces of dihydrofuran (1) affording diastereomeric η2-complexes 7 and 10. Subsequent carbopalladation, followed by β-hydride elimination

Flexible synthesis of anthracycline aglycone mimics via domino carbopalladation reactions

• Markus Leibeling and
• Daniel B. Werz

Beilstein J. Org. Chem. 2013, 9, 2194–2201, doi:10.3762/bjoc.9.258

• Markus Leibeling Daniel B. Werz Institut für Organische Chemie, Technische Universität Braunschweig, Hagenring 30, 38106 Braunschweig, Germany 10.3762/bjoc.9.258 Abstract A synthesis of anthracycline aglycone derivatives is described. The key step utilizes a powerful domino carbopalladation

• different products and a broad range of structural diversity. Keywords: anthracyclines; carbohydrates; carbopalladation; catalysis; domino reaction; natural products; Introduction Anthracyclines are a widespread class of natural products which belong to the group of aromatic polyketides [1]. Most of them

• motif in a few additional steps. Results and Discussion Retrosynthetic strategy After having established several methods of domino carbopalladation reactions which employ dialkynyl-substituted bromoglycals [17][18][19][20] or bromoarenes [21], we envisioned to apply a similar procedure for the

Intramolecular carbolithiation of N-allyl-ynamides: an efficient entry to 1,4-dihydropyridines and pyridines – application to a formal synthesis of sarizotan

• Wafa Gati,
• Mohamed M. Rammah,
• Mohamed B. Rammah and
• Gwilherm Evano

Beilstein J. Org. Chem. 2012, 8, 2214–2222, doi:10.3762/bjoc.8.250

• interest in the chemistry of ynamides [7][8][9][10][11][12][13][14][15][16][17][18] and inspired by recent reports from Meyer and Cossy [19][20][21], Marek [22][23][24] and Lam [25][26] on their carbopalladation, carbocupration and carbozincation, respectively, we decided to study the intramolecular

Recent advances in direct C–H arylation: Methodology, selectivity and mechanism in oxazole series

• Cécile Verrier,
• Pierrik Lassalas,
• Laure Théveau,
• Guy Quéguiner,
• François Trécourt,
• Francis Marsais and
• Christophe Hoarau

Beilstein J. Org. Chem. 2011, 7, 1584–1601, doi:10.3762/bjoc.7.187

• -free, Pd(II)-based catalyst for direct decarboxylative cross-coupling of azole with various benzoic acids (Scheme 26a). In particular, benzoxazole was successfully coupled with 2,6-dimethoxybenzoic acid in 45% yield. Thus, without the assistance of a strong base, a carbopalladation was proposed as a

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

• cyclofunctionalization of the allyl moiety by carbopalladation/reductive elimination [22]. It is interesting to note that 3-sulfonylpyrolidin-2-ones (γ-lactams) 48 may also be accessed in high yield as single trans-diastereomers upon simple treatment of N-allyl- or N-methylpyrrolidines with 2-mercaptobenzoic acid in

• partners through a Pd-mediated allylic amination The allene carbopalladation process with organic halides is known to generate a π-allylpalladium intermediate, which can be trapped by intermolecular carbo- or heteronucleophiles to produce the corresponding three-component adduct. This strategy was used by

• -allenylamines, organic halides and isocyanates [42]. In this process, there is first a carbopalladation of the functionalized allene with the aryl iodide, followed by reaction of the internal aza-nucleophile with the highly electrophilic isocyanate derivative, before premature trapping of the initially formed π