Ligand effects, solvent cooperation, and large kinetic solvent deuterium isotope effects in gold(I)-catalyzed intramolecular alkene hydroamination

• Ruichen Lan,
• Brock Yager,
• Yoonsun Jee,
• Cynthia S. Day and
• Amanda C. Jones

Beilstein J. Org. Chem. 2024, 20, 479–496, doi:10.3762/bjoc.20.43

• molecule of amine delivers a proton to the alkylgold intermediate (for protodeauration). In a platinum-catalyzed hydroamination, a protodemetalation pathway is supported by kinetics and reactivity studies on generated platinum alkyl intermediates [46]. In a palladium-catalyzed hydroamination, a

• protodemetalation pathway is also supported by kinetics and reactivity studies on generated palladium alkyl intermediates [47]. Formation of alkylgold intermediates is known to proceed with anti-attack [27] and the stereospecificity observed in deuterium-labeled intermediates was used as an argument for

• involvement in proton transfer at the transition state [78]. In systems where protodemetalation is rate determining, a metal-carbon bonded intermediate is allegedly characterized, as in the case of a related palladium-catalyzed hydroamination [47], and a propargylamide cyclization [44]. In our studies, the

Mono or double Pd-catalyzed C–H bond functionalization for the annulative π-extension of 1,8-dibromonaphthalene: a one pot access to fluoranthene derivatives

• Nahed Ketata,
• Linhao Liu,
• Ridha Ben Salem and
• Henri Doucet

Beilstein J. Org. Chem. 2024, 20, 427–435, doi:10.3762/bjoc.20.37

• palladium-catalyzed direct intermolecular arylation, followed by a direct intramolecular arylation step. As the C–H bond activation of several benzene derivatives remains very challenging, the preparation of fluoranthenes from 1,8-dibromonaphthalene via Suzuki coupling followed by intramolecular C–H

• ; palladium; Introduction Substituted polyaromatics such as fluoranthenes (Figure 1) are widely used in materials chemistry due to their physical properties, and the introduction of a suitable functional group on the appropriate positions of fluoranthenes either allows their photophysical properties to be

• using commercially available substrates and allowing the regioselective introduction of functional groups at the desired positions is still needed. By using Pd-catalyzed double C–H bond functionalization of activated arenes, such as (poly)fluoroarenes, or by combining a palladium-catalyzed

Mechanisms for radical reactions initiating from N-hydroxyphthalimide esters

• Carlos R. Azpilcueta-Nicolas and
• Jean-Philip Lumb

Beilstein J. Org. Chem. 2024, 20, 346–378, doi:10.3762/bjoc.20.35

• substrate and participating in the key bond-forming/breaking steps via substrate–TM interactions [73][74]. This paradigm has been employed in the activation of NHPI esters under photoinduced copper (Cu) and palladium (Pd) catalysis. In 2017, Peters and Fu reported a Cu-catalyzed decarboxylative C(sp3)–N

Synthesis of π-conjugated polycyclic compounds by late-stage extrusion of chalcogen fragments

• Aissam Okba,
• Pablo Simón Marqués,
• Kyohei Matsuo,
• Naoki Aratani,
• Hiroko Yamada,
• Gwénaël Rapenne and
• Claire Kammerer

Beilstein J. Org. Chem. 2024, 20, 287–305, doi:10.3762/bjoc.20.30

• derivative 21 was synthesized in six steps in 14% overall yield from 3-bromothiophene (17, Scheme 7). In the first step, the sulfur atom embedded in the final thiepine ring was introduced via a palladium-catalyzed S-arylation of 3-bromothiophene in the presence of potassium thioacetate, to afford the

Catalytic multi-step domino and one-pot reactions

• Svetlana B. Tsogoeva

Beilstein J. Org. Chem. 2024, 20, 254–256, doi:10.3762/bjoc.20.25

• through concerted or stepwise mechanisms. An enantioselective palladium-catalyzed three-component reaction of glyoxylic acid, sulfonamides, and aryltrifluoroborates toward synthetically useful α-arylglycine compounds is described by the Manolikakes group [11]. Moreover, Šebesta and co-workers report a

Metal-catalyzed coupling/carbonylative cyclizations for accessing dibenzodiazepinones: an expedient route to clozapine and other drugs

• Amina Moutayakine and
• Anthony J. Burke

Beilstein J. Org. Chem. 2024, 20, 193–204, doi:10.3762/bjoc.20.19

• (DBDAPs) is disclosed in this article through a palladium and copper-catalyzed amination (Buchwald–Hartwig (B–H) or Chan–Lam (C–L)) followed by a palladium-catalyzed intramolecular aminocarbonylation with Mo(CO)6 as CO surrogate (to avoid toxic CO handling) of readily available o-phenylenediamines and

• via a cross-coupling reaction with NH3 [13]. The reaction was undertaken in the presence of a catalytic amount of a palladium catalyst and afforded a library of dibenzodiazepinones in good to excellent yields (Scheme 1a). In 2013, Zhang et al. developed a synthetic route leading to structurally

• strategy was reported by Laha et al., aiming to access dibenzodiazepinone structures via a double N-arylation of 2-aminobenzamides with 1,2-dihaloarenes using a palladium-based catalytic system [15]. Mechanistic investigations supported the fact that the regioselective N-arylation of the 2-aminobenzamide

Biphenylene-containing polycyclic conjugated compounds

• Cagatay Dengiz

Beilstein J. Org. Chem. 2023, 19, 1895–1911, doi:10.3762/bjoc.19.141

• . In this context, Xia and co-workers drew inspiration from their prior investigations on palladium-catalyzed annulation reactions concerning ladder polymers [37]. They envisioned that by making minor modifications to the starting materials, they could readily access structurally complex POAs. The

• researchers efficiently conducted palladium-catalyzed C–H activated annulation reactions, involving oxanorbornadiene derivative 26 and aryl bromides including dibromoanthracene 27 [38]. Subsequent aromatization reactions were then carried out, resulting in the successful synthesis of the target POAs with high

• 34a-TIPS showed hole mobilities of 0.075 cm2 V−1 s−1 and 0.19 cm2 V−1 s−1, respectively, while the highest value was noted with 34a-TIBS at 0.52 cm2 V−1 s−1. Later on, Xia and his colleagues demonstrated that curved PAH structures can be synthesized by employing their own developed palladium-catalyzed

Aromatic systems with two and three pyridine-2,6-dicarbazolyl-3,5-dicarbonitrile fragments as electron-transporting organic semiconductors exhibiting long-lived emissions

• Karolis Leitonas,
• Brigita Vigante,
• Dmytro Volyniuk,
• Audrius Bucinskas,
• Pavels Dimitrijevs,
• Sindija Lapcinska,
• Pavel Arsenyan and
• Juozas Vidas Grazulevicius

Beilstein J. Org. Chem. 2023, 19, 1867–1880, doi:10.3762/bjoc.19.139

• equiv), tetrakis(triphenylphosphine)palladium(0) (11.6 mg, 0.01 mmol, 0.05 equiv), CuI (1.2 mg, 0.006 mmol, 0.03 equiv) in 2 mL of DMF was degassed with Ar. Then, the appropriate ethynyl derivative (0.24 mmol, 1.2 equiv) and 1 mL of triethylamine were added and the resulting mixture was heated at 90 °C

Thienothiophene-based organic light-emitting diode: synthesis, photophysical properties and application

• Recep Isci and
• Turan Ozturk

Beilstein J. Org. Chem. 2023, 19, 1849–1857, doi:10.3762/bjoc.19.137

• ), dimesitylboronfluoride (90%, Sigma-Aldrich), 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Sigma-Aldrich), tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4, 99%, Sigma-Aldrich), were used as received. Diethyl ether and THF were dried over metallic sodium. Dimethylformamide (HPLC grade) was stored over activated molecular

Synthetic approach to 2-alkyl-4-quinolones and 2-alkyl-4-quinolone-3-carboxamides based on common β-keto amide precursors

• Yordanka Mollova-Sapundzhieva,
• Plamen Angelov,
• Danail Georgiev and
• Pavel Yanev

Beilstein J. Org. Chem. 2023, 19, 1804–1810, doi:10.3762/bjoc.19.132

• of methods for their synthesis is a very active area of research. Recent contributions to the synthesis of 4-quinolones made use of phosphine-mediated redox cyclization of 1-(2-nitroaryl)prop-2-ynones [39], palladium-catalyzed carbonylative cyclization of 2-bromonitrobenzenes and alkynes [40], TsCl

• , limiting the reaction time to 60–90 min under these conditions allowed some of the N-hydroxy derivatives 4 to be isolated in good yield (Table 5), even though it did not entirely prevent the formation of products 5. Palladium catalysis was not appropriate for the hydrogenation of compounds 3f and 3g

• , because of concomitant reduction at the C–Cl bond. Intermediates 6, similarly to compounds 3, gave mixtures of products 7/8 under palladium-catalyzed transfer hydrogenation conditions. In contrast to 3, however, limiting the reaction time here did not help to develop a preparatively useful procedure for a

Tying a knot between crown ethers and porphyrins

• Maksym Matviyishyn and
• Bartosz Szyszko

Beilstein J. Org. Chem. 2023, 19, 1630–1650, doi:10.3762/bjoc.19.120

• molecule bound to the cobalt(III) outside the Pacman cleft and the crown ether part of the adjacent molecule. The type and properties of the coordination compound formed from 16–19 depended strongly on the size and structure of the crown ether part of the molecule and the transition metal [67]. Palladium

• (II) compounds 16-Pd–19-Pd exhibited conformations with the characteristic Pacman clefts, resembling their postulated solution structures and typical square-planar geometry around the palladium(II) centres. Titanium(III), vanadium(III), and chromium(III) complexes were synthesised through salt

• geometry with the cobalt(II) positioned slightly above the N4 donor plane. The X-ray structure of 18b-Co exhibited a similar Pacman motif as its palladium analogue, with the cobalt(II) cation residing in a square-planar environment. The exploitation of a similar synthetic methodology allowed for preparing

Synthesis of 7-azabicyclo[4.3.1]decane ring systems from tricarbonyl(tropone)iron via intramolecular Heck reactions

• Aaron H. Shoemaker,
• Elizabeth A. Foker,
• Elena P. Uttaro,
• Sarah K. Beitel and
• Daniel R. Griffith

Beilstein J. Org. Chem. 2023, 19, 1615–1619, doi:10.3762/bjoc.19.118

• vast body of knowledge built from many synthetic campaigns towards the Strychnos alkaloids [15]. Several combinations of palladium catalyst, base, and other additives were applied to our system (see Table 1, entries 1–4). Reaction conditions such as those deployed to great effect by Rawal [16] (Table 1

• cleanly according to TLC analysis, but the isolated yield of the intramolecular Heck product was low, perhaps due to instability of one of the intermediate palladium complexes and/or a slow olefin insertion step. Moreover, the product was obtained as an inseparable mixture of the allylic carbamate 18 and

Synthesis and biological evaluation of Argemone mexicana-inspired antimicrobials

• Jessica Villegas,
• Bryce C. Ball,
• Katelyn M. Shouse,
• Caleb W. VanArragon,
• Ashley N. Wasserman,
• Hannah E. Bhakta,
• Allen G. Oliver,
• Danielle A. Orozco-Nunnelly and
• Jeffrey M. Pruet

Beilstein J. Org. Chem. 2023, 19, 1511–1524, doi:10.3762/bjoc.19.108

• berberine variants none are as easily modulated to rapidly install substituent diversity [31][43][44][45][46][47][48]. The method deemed most amenable to varying substituents involves substituted 2-bromo-1-aminonaphthalenes which are used in subsequent palladium cross-coupling reactions [45]. As such, our

N-Sulfenylsuccinimide/phthalimide: an alternative sulfenylating reagent in organic transformations

• Fatemeh Doraghi,
• Seyedeh Pegah Aledavoud,
• Mehdi Ghanbarlou,
• Bagher Larijani and
• Mohammad Mahdavi

Beilstein J. Org. Chem. 2023, 19, 1471–1502, doi:10.3762/bjoc.19.106

• succeeded in synthesizing various diaryl(alkyl) sulfides 5 through the sulfenylation of unactivated arenes 4 with an electrophilic sulfur reagent in the presence of a palladium catalyst (Scheme 3) [45]. In the second phase, dibenzothiophene derivatives 6 were obtained via subsequent intramolecular arylation

• this work. In 2018, Anbarasan and Chaitanya developed an efficient approach for the C–H bond functionalization of aryl compounds containing a directing group using N-(thioaryl)phthalimides 14 in the presence of a palladium catalyst (Scheme 15) [53]. The thiolation occurred in the presence of Pd(OAc)2

• , respectively. It should be noted that the use of a palladium catalyst was essential for the cross-coupling reaction between 1’’’ and 74. Also, the presence of ZnCl2 could facilitate the cleavage of the N–S bond. In the case of amines and thiols, there was no need for a metal catalyst for the formation of S–N

One-pot nucleophilic substitution–double click reactions of biazides leading to functionalized bis(1,2,3-triazole) derivatives

• Hans-Ulrich Reissig and
• Fei Yu

Beilstein J. Org. Chem. 2023, 19, 1399–1407, doi:10.3762/bjoc.19.101

• transformation into divalent carbohydrate mimetics turned out to be a difficult task. We started the experiments with the hydrogenolysis of bicyclic 1,2-oxazin-4-ol 19 as simple model compound (Scheme 7). A methanol solution of 19 under an atmosphere of hydrogen was stirred for 17 h in the presence of palladium

• -triazole) 21. It turned out that the hydrogenolysis of this compound was very capricious and (in part) depended on the batch of palladium on carbon used. In most cases, incomplete consumption of starting material was observed, even after long reaction time. The best result is depicted in Scheme 8 (reaction

• 1), when after five days of hydrogenolysis and 0.8 equivalents of palladium at least 40% of impure divalent aminopyran derivative 25 was isolated. The major component of the isolated material is certainly fitting to the proposed structure according to the NMR data and their comparison with related

Synthesis of ether lipids: natural compounds and analogues

• Marco Antônio G. B. Gomes,
• Alicia Bauduin,
• Chloé Le Roux,
• Romain Fouinneteau,
• Wilfried Berthe,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96

Radical ligand transfer: a general strategy for radical functionalization

• David T. Nemoto Jr,
• Kang-Jie Bian,
• Shih-Chieh Kao and
• Julian G. West

Beilstein J. Org. Chem. 2023, 19, 1225–1233, doi:10.3762/bjoc.19.90

• literature examples of nitrate oxidation of different transition metals, such as palladium. Control reactions further supported this proposal, including the inability of alternative Fe(III) salts (e.g., FeCl3) to form more than stoichiometric azide product in the absence of added nitrate. We believe this

Copper-catalyzed N-arylation of amines with aryliodonium ylides in water

• Kasturi U. Nabar,
• Bhalchandra M. Bhanage and
• Sudam G. Dawande

Beilstein J. Org. Chem. 2023, 19, 1008–1014, doi:10.3762/bjoc.19.76

• development since the pioneering work by Ullmann [13] and Goldberg [14]. Despite the significant advances, the main limitations are the harsh reaction conditions such as high temperatures, pressure, and unsustainability which limits their scalability for industrial applications. Further, palladium-catalyzed

• strategies for C–N bond formation have been extensively explored by various research groups for the N-arylation of amines. Specifically, seminal contributions by Buchwald [15] and Hartwig [16] involving the use of palladium complexes as catalysts in the presence of either phosphine or diamine ligands for C–N

• bond formation. However, these methods suffer from limitations such as moisture sensitivity, the requirement of specific ligands, and the use of expensive palladium catalysts [17]. Also, Chan Lam, Evans, and other research groups have developed copper-catalyzed C–N bond formation reactions by careful

Photoredox catalysis enabling decarboxylative radical cyclization of γ,γ-dimethylallyltryptophan (DMAT) derivatives: formal synthesis of 6,7-secoagroclavine

• Alessio Regni,
• Francesca Bartoccini and
• Giovanni Piersanti

Beilstein J. Org. Chem. 2023, 19, 918–927, doi:10.3762/bjoc.19.70

• ]. Regioselective palladium-catalyzed prenylation of 2 with prenylboronic acid pinacol ester and subsequent hydrolysis with LiOH provided the linear prenylated acid 4 in good yield. Coupling acid 4 with N-hydroxyphthalimide using DCC and a catalytic amount of DMAP afforded the key intermediate 5 in 59% yield. With

Light-responsive rotaxane-based materials: inducing motion in the solid state

• Adrian Saura-Sanmartin

Beilstein J. Org. Chem. 2023, 19, 873–880, doi:10.3762/bjoc.19.64

• direction, one potential strategy is the approach followed by Feringa and co-workers [72], in which palladium-porphyrin photosensitizer-based struts were employed within a metal-organic material, allowing the use of green light as irradiation source because of the effective energy transfer between these

Pyridine C(sp²)–H bond functionalization under transition-metal and rare earth metal catalysis

• Haritha Sindhe,
• Malladi Mounika Reddy,
• Karthikeyan Rajkumar,
• Akshay Kamble,
• Amardeep Singh,
• Anand Kumar and
• Satyasheel Sharma

Beilstein J. Org. Chem. 2023, 19, 820–863, doi:10.3762/bjoc.19.62

• ). In 2015, a palladium-catalyzed cross dehydrogenative coupling of pyridine N-oxides with toluene for the regioselective arylation and benzylation of pyridine N-oxide was reported by Khan and co-workers [92] (Scheme 23). The authors have shown toluene 117 when used as benzyl and aryl source remained

• N-oxide 119b. In 2016, Wei and co-workers [93] reported the arylation of pyridine N-oxides 9 employing potassium (hetero)aryltrifluoroborates 126 as coupling partner using palladium acetate and TBAI (Scheme 24). Electron-withdrawing and donating groups on the pyridine N-oxide 9 resulted in the

• hydrolyzed to get the corresponding ketones. In 2018, Albéniz and group [99] reported the direct C3-arylation of pyridines with the help of bipy-6-OH as coordinating ligand under palladium catalysis (Scheme 29). In most of the cases the arylated pyridines 152 were obtained as mixtures of ortho-/meta-/para

Palladium-catalyzed enantioselective three-component synthesis of α-arylglycine derivatives from glyoxylic acid, sulfonamides and aryltrifluoroborates

• Bastian Jakob,
• Nico Schneider,
• Luca Gengenbach and
• Georg Manolikakes

Beilstein J. Org. Chem. 2023, 19, 719–726, doi:10.3762/bjoc.19.52

• Bastian Jakob Nico Schneider Luca Gengenbach Georg Manolikakes Department of Chemistry, RPTU Kaiserslautern-Landau, Erwin-Schrödinger-Str. Geb. 54, D-67663 Kaiserslautern, Germany 10.3762/bjoc.19.52 Abstract A palladium-catalyzed enantioselective three-component reaction of glyoxylic acid

• products. Keywords: amino acids; asymmetric catalysis; multicomponent reaction; palladium catalysis; Petasis reaction; sulfonamides; Introduction α-Amino acids play a crucial role in every aspect of our human life [1]. They are important synthetic intermediates in the chemical industry and used for the

• palladium-catalyzed three-component reactions between arylboronic or carboxylic acids, amides or sulfonamides and different aldehyde components as attractive and broadly applicable alternative to the classical Petasis borono-Mannich reaction (Scheme 1b) [17][18][19][20][21]. Recently, we were able to extend

Strategies in the synthesis of dibenzo[b,f]heteropines

• David I. H. Maier,
• Barend C. B. Bezuidenhoudt and
• Charlene Marais

Beilstein J. Org. Chem. 2023, 19, 700–718, doi:10.3762/bjoc.19.51

• synthesised via a copper-catalysed Ullman-type coupling or a palladium-catalysed Buchwald–Hartwig amination (Scheme 9). Performing the rearrangement at high temperatures resulted in the undesirable formation of acridine byproducts 44. Cleaner reaction profiles could be obtained at a lower temperature (100 °C

• thioethers from aryl halides and triflates through palladium catalysis [50][51]. Scheme 10 provides a retrosynthesis of amination in the synthesis of dibenzo[b,f]azepine 45 as an example. Arnold et al. [30] reported an excellent method for the convergent synthesis of variable sized dibenzo-fused heterocycles

• precursor 102 and the complementary aldehyde 103. 3.4 Catellani-type reaction The Catellani reaction involves palladium-norbornene cooperative catalysis to functionalise the ortho- and ipso-positions of aryl halides by alkylation, arylation, amination, acylation, thiolation, etc. [63]. Della Ca' et al. [64

Synthesis of medium and large phostams, phostones, and phostines

• Jiaxi Xu

Beilstein J. Org. Chem. 2023, 19, 687–699, doi:10.3762/bjoc.19.50

• -methylphenyl)benzothiophene-fused 2-hydroxy-1-oxa-2-phosphacycloundecane 2-oxide 36 in 83% yield (Scheme 7) [22]. 1.1.2 Synthesis via other C–C bond formations: The palladium-catalyzed intramolecular Heck arylation of 2-bromophenylmethyl alk-1-enylphosphinates 37 provides access to 4-alkylidene-1,4

• palladium-catalyzed intramolecular arylation of 3-(2-bromophenyl)propyl alkylphosphinates 61 approached the synthesis of 3,4,5-trihydrobenzo[c][1,2]oxaphosphepine 1-oxides 62 in moderate 39–45% yields in the presence of triethylamine in dry toluene at 100 °C [33]. When the substrates were extended to 5

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

• sketched in red, with newly formed cyclic structures being highlighted. Review Earth-abundant metals Among the transition metal used in organic synthesis, the late transition metals like rhodium, palladium, and iridium have taken center stage when it comes to methodology development. Although these late

• ][19][20][21][22][23][24][25][26][27]. In this section, we summarize recent progress in Ni, Fe, Cu, and Co-catalyzed domino reactions of strained bicyclic alkenes. Nickel-catalyzed reactions Without close inspection, nickel might seem like the peculiar younger sibling of palladium within the field of

• transition-metal catalysis. Nickel lies directly above palladium in the periodic table, as such, it readily performs many of the same elementary reactions. Because of their reactive commonalties, nickel is often seen as the budget-friendly replacement; however, this misconception will clearly be refuted in