Advancements in hydrochlorination of alkenes

• Daniel S. Müller

Beilstein J. Org. Chem. 2024, 20, 787–814, doi:10.3762/bjoc.20.72

• , requiring four steps, coupled with the expense of the palladium catalyst. Interestingly, when the hydroxy group in L3 was protected, the chemoselectivity of the reaction was poor, resulting in a 1:2 mixture of the desired chloride and the corresponding terminal alkene. Liu and colleagues put forth 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

• 1,8-dibromonaphthalene, 1,3-dichlorobenzene led to 7,9-dichlorofluoranthene (15) with a yield of 38%. We have previously described the reaction of 1,8-dibromonaphthalene with some heteroarenes such as 2-methylthiophene in the presence of a palladium catalyst for the synthesis of acenaphtho[1,2-d

• with 1,2-dihalobenzenes. To our knowledge, this reaction has not yet been described, but 9-arylphenanthrenes can be synthesized by reacting 1-bromo-2-(1-phenylthenyl)benzene with bromobenzenes as coupling partners in the presence of a palladium catalyst [41]. We have observed that the reaction of 3

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

• 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

• carbonylative intramolecular cyclization of the intermediate 3a using different catalytic systems. To elucidate the role of the palladium catalyst in this process, we carried out the initial attempt under metal free-conditions using molybdenum hexacarbonyl (Mo(CO)6) as CO surrogate, in the presence of Et3N in

• elimination of the palladium catalyst. Conclusion In summary, we have reported two one-pot pathways and two step-wise pathways to access dibenzodiazepinone (DBDAP) derivatives via copper-catalyzed Chan–Lam amination/carbonylative cyclization and Buchwald–Hartwig amination/carbonylative cyclization and their

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

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

Transition-metal-catalyzed C–H bond activation as a sustainable strategy for the synthesis of fluorinated molecules: an overview

• Louis Monsigny,
• Floriane Doche and
• Tatiana Besset

Beilstein J. Org. Chem. 2023, 19, 448–473, doi:10.3762/bjoc.19.35

• involved in most cases an electrophilic SCF3 source (R1R2NSCF3). For these transformations, the following working hypothesis was generally suggested (Scheme 4). After coordination of the palladium catalyst to a directing group, the metallacycle A is formed. This latter undergoes an oxidative addition in

• the presence of an electrophilic source or an oxidation/ligand exchange in the presence of a nucleophilic source (i.e., AgSCF3) and an oxidant (B in Scheme 4). Finally, after a reductive elimination step, the expected functionalized product 6 is obtained and the palladium catalyst is regenerated. In

• to the formation of the species S. The latter complex S undergoes a reductive elimination leading to the compound 48’ along with the regeneration of the palladium catalyst. Finally, after hydrolysis of 48’, the expected product 48 is afforded together with the organocatalyst. Then, the group of Sun

Synthesis of odorants in flow and their applications in perfumery

• Merlin Kleoff,
• Paul Kiler and
• Philipp Heretsch

Beilstein J. Org. Chem. 2022, 18, 754–768, doi:10.3762/bjoc.18.76

• Lindlar catalyst containing toxic lead salts, selectivity is achieved by the improved reaction control in flow. A solution of alkyne 31 in methanol is mixed with a stream of hydrogen and pumped at room temperature and 2.5 bar through a tubular glass column containing a Dowex-supported palladium catalyst

• ) via selective hydrogenation to enone 27, condensation to hydrazone 28 and subsequent Shapiro reaction. DMPS = dimethylpolysilane-modified platinum catalyst; Ts = tosyl. Selective hydrogenation of alkyne 31 to “leaf alcohol” 32 employing a solid-supported palladium catalyst. A) Synthesis of jasmonal

Ligand-dependent stereoselective Suzuki–Miyaura cross-coupling reactions of β-enamido triflates

• Tomáš Chvojka,
• Athanasios Markos,
• Svatava Voltrová,
• Radek Pohl and
• Petr Beier

Beilstein J. Org. Chem. 2021, 17, 2657–2662, doi:10.3762/bjoc.17.179

• 43 Prague 2, Czech Republic 10.3762/bjoc.17.179 Abstract The stereoselective Suzuki–Miyaura cross-coupling of (Z)-β-enamido triflates is demonstrated. Depending on the nature of the ligand in the palladium catalyst, either retention or inversion of the configuration during the synthesis of β,β

α-Ketol and α-iminol rearrangements in synthetic organic and biosynthetic reactions

• Scott Benz and
• Andrew S. Murkin

Beilstein J. Org. Chem. 2021, 17, 2570–2584, doi:10.3762/bjoc.17.172

• ring strain from cyclobutane derivatives has been developed by Cheng et al. to prepare functionalized α-amino cyclopentanones [31]. In the presence of a palladium catalyst, an electron-rich heteroarene 115 first adds to the nitrile group in a 1-cyanocyclobutyl ester 116 to give a tetrahedral imine

Facile and innovative catalytic protocol for intramolecular Friedel–Crafts cyclization of Morita–Baylis–Hillman adducts: Synergistic combination of chiral (salen)chromium(III)/BF₃·OEt₂ catalysis

• Karthikeyan Soundararajan,
• Helen Ratna Monica Jeyarajan,
• Raju Subimol Kamarajapurathu and
• Karthik Krishna Kumar Ayyanoth

Beilstein J. Org. Chem. 2021, 17, 2186–2193, doi:10.3762/bjoc.17.140

• presence of a palladium catalyst from allylic acetates of MBH adducts. Recently Anas et al. [14] has reported the palladium-catalysed synthesis of indene from MBH adducts at 120 °C under N2 atmosphere. The methodologies referred in Scheme 1 access indenes either relying on harsh reaction conditions or on

A recent overview on the synthesis of 1,4,5-trisubstituted 1,2,3-triazoles

• Pezhman Shiri,
• Ali Mohammad Amani and
• Thomas Mayer-Gall

Beilstein J. Org. Chem. 2021, 17, 1600–1628, doi:10.3762/bjoc.17.114

• synthesis of fully decorated 1,2,3-triazoles 162, 164, and 166 was reported by Ackermann et al. via intramolecular oxidative C–H arylation of 1,2,3-triazoles 161, 163, and 165 using a reusable palladium catalyst in PEG, Pd@PEG, under O2 atmosphere. The main advantages of this strategy include i) a versatile

• methodology for aerobic C–H activation; ii) PEG as green and recyclable reaction medium; and iii) a reusable palladium catalyst complex [65]. Fully functionalized 1,2,3-triazolo-fused chromenes 162, 164, and 166 were regioselectively prepared in moderate yield. The isoindoline-fused triazoles 164 were

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

• Guido Gambacorta,
• James S. Sharley and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90

Manganese/bipyridine-catalyzed non-directed C(sp³)–H bromination using NBS and TMSN₃

• Kumar Sneh,
• Takeru Torigoe and
• Yoichiro Kuninobu

Beilstein J. Org. Chem. 2021, 17, 885–890, doi:10.3762/bjoc.17.74

• -position of an oxazoline or amide is selectively activated using a copper or palladium catalyst. Manganese is one of the most abundant and nontoxic transition metals found in the earth’s crust and its corresponding complexes and salts are useful in synthetic organic reactions [29][30][31][32][33][34][35

Helicene synthesis by Brønsted acid-catalyzed cycloaromatization in HFIP [(CF₃)₂CHOH]

• Takeshi Fujita,
• Noriaki Shoji,
• Nao Yoshikawa and
• Junji Ichikawa

Beilstein J. Org. Chem. 2021, 17, 396–403, doi:10.3762/bjoc.17.35

• -catalyzed cycloaromatization (Scheme 3, route a and Scheme 4a). Treatment of 1,2-dibromobenzene (2a) with 3 in the presence of a palladium catalyst with SPhos afforded o-terphenyl derivative 4a bearing two acetal groups in 96% yield (Scheme 4a). The obtained bisacetal 4a successfully underwent

• subsequent cycloaromatization (Scheme 6a). Again, phenylboronic acid ester 3, used above in the synthesis of [5]- and [6]helicenes, was adopted as the coupling partner for 10. In the presence of a palladium catalyst, treatment of 3-bromobenzofuran (10a), 3-bromobenzothiophene (10b), and 3-bromo(N-tosyl

Bifurcated synthesis of methylene-lactone- and methylene-lactam-fused spirolactams via electrophilic amide allylation of γ-phenylthio-functionalized γ-lactams

• Tetsuya Sengoku,
• Koki Makino,
• Ayumi Iijima,
• Toshiyasu Inuzuka and
• Hidemi Yoda

Beilstein J. Org. Chem. 2020, 16, 2769–2775, doi:10.3762/bjoc.16.227

• sodium hydride, affording the corresponding adduct in 50% and 81% yields, respectively (Table 1, entries 6 and 7). Surprisingly, the desired allylation underwent even in the absence of palladium catalyst, probably due to high nucleophilicity of the deprotonated intermediate, to give 3b in 87% yield

Aryl-substituted acridanes as hosts for TADF-based OLEDs

• Naveen Masimukku,
• Dalius Gudeika,
• Oleksandr Bezvikonnyi,
• Ihor Syvorotka,
• Rasa Keruckiene,
• Dmytro Volyniuk and
• Juozas V. Grazulevicius

Beilstein J. Org. Chem. 2020, 16, 989–1000, doi:10.3762/bjoc.16.88

• presence of a palladium catalyst, with yields ranging from 27 to 50%. The chemical structures of 3–6 were confirmed by 1H and 13C NMR spectroscopy, elemental analysis and mass spectrometry. Transparent thin films of these compounds could be prepared by vacuum evaporation or by spin coating from solutions

Pd-catalyzed asymmetric Suzuki–Miyaura coupling reactions for the synthesis of chiral biaryl compounds with a large steric substituent at the 2-position

• Yongsu Li,
• Bendu Pan,
• Xuefeng He,
• Wang Xia,
• Yaqi Zhang,
• Hao Liang,
• Chitreddy V. Subba Reddy,
• Rihui Cao and
• Liqin Qiu

Beilstein J. Org. Chem. 2020, 16, 966–973, doi:10.3762/bjoc.16.85

• bromobenzene substrates and the Pd···O interaction between carbonyl and palladium seem essential to achieve high enantioselectivity. Keywords: asymmetric catalysis; biaryls; monophosphine ligand; palladium catalyst; Suzuki–Miyaura couplings; Introduction Axially chiral molecules have received much attention

Formal preparation of regioregular and alternating thiophene–thiophene copolymers bearing different substituents

• Atsunori Mori,
• Keisuke Fujita,
• Chihiro Kubota,
• Toyoko Suzuki,
• Kentaro Okano,
• Takuya Matsumoto,
• Takashi Nishino and
• Masaki Horie

Beilstein J. Org. Chem. 2020, 16, 317–324, doi:10.3762/bjoc.16.31

• -substituted thiophene 3 efficiently gave chlorobithiophene 4 in a facile manner (Scheme 2) [25]. The use of a palladium catalyst efficiently suppressed the undesired polymerization to afford the HT halobithiophene with different substituents [26]. Compared to an alternative pathway to 4, in which initial

A new approach to silicon rhodamines by Suzuki–Miyaura coupling – scope and limitations

• Thines Kanagasundaram,
• Antje Timmermann,
• Carsten S. Kramer and
• Klaus Kopka

Beilstein J. Org. Chem. 2019, 15, 2569–2576, doi:10.3762/bjoc.15.250

• gave access to silicon rhodamines in poor to moderate yields, we wanted to improve these first valuable experimental results. Results: The preparation of the xanthene triflate was enhanced and several boron sources were screened to find the optimal coupling partner. After optimization of the palladium

• catalyst, different substituted boroxines were assessed to explore the scope of the Pd-catalyzed cross-coupling reaction. Conclusions: A number of silicon rhodamines were synthesized under the optimized conditions in up to 91% yield without the necessity of HPLC purification. Moreover, silicon rhodamines

Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

• Xiaowei Li,
• Xiaolin Shi,
• Xiangqian Li and
• Dayong Shi

Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218

• a palladium catalyst (Scheme 9). Under these conditions, the fluorination of ethyl 2-cyano-2-phenylacetate afforded the product with highest enantiomeric excess (93%). In 2013, Kim’s group [46] described an enantioselective electrophilic fluorination of α-chloro-β-keto phosphonates with up to 95% ee

Recent advances on the transition-metal-catalyzed synthesis of imidazopyridines: an updated coverage

• Gagandeep Kour Reen,
• Ashok Kumar and
• Pratibha Sharma

Beilstein J. Org. Chem. 2019, 15, 1612–1704, doi:10.3762/bjoc.15.165

Synthesis of dipolar molecular rotors as linkers for metal-organic frameworks

• Sebastian Hamer,
• Fynn Röhricht,
• Marius Jakoby,
• Ian A. Howard,
• Xianghui Zhang,
• Christian Näther and
• Rainer Herges

Beilstein J. Org. Chem. 2019, 15, 1331–1338, doi:10.3762/bjoc.15.132

• -trimethylsilyl-2-tributylstannylacetylene in combination with the bulky palladium catalyst bis(tri-tert-butylphosphino)palladium. The TMS-protected, dicyano-substituted rotors with thiadiazole, dioxole and dioxane annelation 12a, and 16 were prepared in yields exceeding 90%. Thus, the dipolar rotors 1–5 are now

Multicomponent reactions (MCRs): a useful access to the synthesis of benzo-fused γ-lactams

• Edorta Martínez de Marigorta,
• Jesús M. de Los Santos,
• Ana M. Ochoa de Retana,
• Javier Vicario and
• Francisco Palacios

Beilstein J. Org. Chem. 2019, 15, 1065–1085, doi:10.3762/bjoc.15.104

• reaction of propiolic acid and aryl halides [78]. Furthermore, the authors have been able to carry out the reaction in a sequential manner starting from propiolic acid and aryl iodides in the presence of caesium carbonate and a palladium catalyst. Next, addition of 2-iodobenzoic acid and ammonium acetate

• , leading to final lactams 20. This mechanism is partially corroborated by the following multicomponent synthesis where benzamide 21, ortho-functionalized with a terminal alkyne group (Scheme 5), a secondary amine 22 and carbon monoxide (23) react to produce 3-methyleneisoindolinones 24 [80]. A palladium

• catalyst in acetonitrile, and a high pressure of both, CO and air, are needed in order to perform an oxidative carbonylation on 2-ethynylbenzamide 21. Up to ten compounds were obtained with yields ranging from 65 to 96%. Butyl, phenyl, benzyl or absence of substitution on the amide nitrogen produced, in

A novel and efficient synthesis of phenanthrene derivatives via palladium/norbornadiene-catalyzed domino one-pot reaction

• Yue Zhong,
• Wen-Yu Wu,
• Shao-Peng Yu,
• Tian-Yuan Fan,
• Hai-Tao Yu,
• Nian-Guang Li,
• Zhi-Hao Shi,
• Yu-Ping Tang and
• Jin-Ao Duan

Beilstein J. Org. Chem. 2019, 15, 291–298, doi:10.3762/bjoc.15.26

• (PPh3)4/PPh3 as the catalyst, Cs2CO3 as base, and dimethyl formamide (DMF) as solvent at 105 °C for 10 h under N2 atmosphere. Meanwhile, different pallladium species were tested in this reaction system. It was found that Pd(OAc)2 was the most effective palladium catalyst, and the desired product y-1 was

Synergistic approach to polycycles through Suzuki–Miyaura cross coupling and metathesis as key steps

• Sambasivarao Kotha,
• Milind Meshram and
• Chandravathi Chakkapalli

Beilstein J. Org. Chem. 2018, 14, 2468–2481, doi:10.3762/bjoc.14.223

• useful protocol to build indene derivatives by employing SM coupling and RCM in sequence. To this end, the SM coupling of triflate 7 was accomplished by using pinacol boronic ester 8 in the presence of a palladium catalyst to give the cross-coupling product 9 (75%). Later on, exposure of the diolefinic

• -workers [33] demonstrated an efficient route for the construction of the benz[a]anthracene structural unit by employing SM cross coupling followed by RCM sequence. Treatment of the bromonaphthalene derivative 20 with (2-formyl-4-methoxyphenyl)boronic acid (21) in the presence of a palladium catalyst

• adopting SM coupling and RCM as key steps. In this respect, SM coupling of sulfoximine 65 with potassium vinyltrifluoroborate (66) in the presence of a palladium catalyst produced vinyl sulfoximine derivative 67 (73%). Next, N-alkenylation of sulfoximine 67 was accomplished with Z-vinyl bromide (68) to