Bipyrrole boomerangs via Pd-mediated tandem cyclization–oxygenation. Controlling reaction selectivity and electronic properties

• Liliia Moshniaha,
• Marika Żyła-Karwowska,
• Joanna Cybińska,
• Piotr J. Chmielewski,
• Ludovic Favereau and
• Marcin Stępień

Beilstein J. Org. Chem. 2020, 16, 895–903, doi:10.3762/bjoc.16.81

• obtained by tandem cyclodehydrogenations of oligoaryl precursors [1][2][3]. This general strategy is attractive because it does not require prefunctionalization of coupling sites and because it provides rapid access to complex π systems. Such cyclodehydrogenations can be performed using diverse oxidants [4

Cascade trifluoromethylthiolation and cyclization of N-[(3-aryl)propioloyl]indoles

• Ming-Xi Bi,
• Shuai Liu,
• Yangen Huang,
• Xiu-Hua Xu and
• Feng-Ling Qing

Beilstein J. Org. Chem. 2020, 16, 657–662, doi:10.3762/bjoc.16.62

• knowledge, the combination of bis(trifluoromethylthiolation) [36][39][40][41] and cascade cyclization reactions has not been reported before. Thus, the amounts of AgSCF3 and K2S2O8 were increased to deliver 2a in 52% yield (Table 1, entry 2). Other oxidants including Na2S2O8 and (NH4)2S2O8 afforded 2a in

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

• ]. While many direct arylation systems occur under neutral conditions and without the need for strong oxidants or reductants, only few proceed at ambient temperatures [3][6]. To our knowledge, only one example of room-temperature DArP exists, namely polymerizing poly-3-hexylthiophene to an acceptably high

Recent developments in photoredox-catalyzed remote ortho and para C–H bond functionalizations

• Rafia Siddiqui and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 248–280, doi:10.3762/bjoc.16.26

• dependence on external oxidants and harsh reaction conditions [83][84]. In this context, in 2014, Fabry et al. reported the use of novel dual photoredox catalytic systems made up of photoredox catalyst 11 and a rhodium catalyst to carry out the Weinreb amide C–H olefination shown in Scheme 1 [85]. By using

• out without the requirement of a proton acceptor or external oxidant, and hydrogen gas was obtained as the only side product (Scheme 6). This was a major achievement since the previously reported methods suffered from undesirable side products and the requirement of oxidants [102][103]. After the use

• oxidants [151][152][153]. To overcome these drawbacks, recently, Cho’s group synthesized carbazole derivatives using a dual photoredox-catalyzed intramolecular C−H bond amination of N-substituted 2-amidobiaryls with photoredox catalyst 14 in presence of Pd(OAc)2 as a cocatalyst under aerobic conditions

Synthesis of 3-alkenylindoles through regioselective C–H alkenylation of indoles by a ruthenium nanocatalyst

• Abhijit Paul,
• Debnath Chatterjee,
• Srirupa Banerjee and
• Somnath Yadav

Beilstein J. Org. Chem. 2020, 16, 140–148, doi:10.3762/bjoc.16.16

• -withdrawing groups, using Pd(OAc)2 as catalyst and Cu(OAc)2 as oxidant [25]. Since then, several variants of the reaction involving Pd catalysis and various oxidants have been reported for the synthesis of 3-alkenylindoles. For example, Chen et al. and Huang et al. independently reported the C3 alkenylation

• carried out employing indole (1a), methyl acrylate (2a), and 3 mg of the RuNC. Different oxidants as well as solvents were explored for the reaction. From the optimisation reactions and the control experiments, it was concluded that the reaction with Cu(OAc)2 as the oxidant in DMF/DMSO, 9:1, v/v at 130 °C

Construction of trisubstituted chromone skeletons carrying electron-withdrawing groups via PhIO-mediated dehydrogenation and its application to the synthesis of frutinone A

• Qiao Li,
• Chen Zhuang,
• Donghua Wang,
• Wei Zhang,
• Rongxuan Jia,
• Fengxia Sun,
• Yilin Zhang and
• Yunfei Du

Beilstein J. Org. Chem. 2019, 15, 2958–2965, doi:10.3762/bjoc.15.291

• reagents have emerged as a class of efficient and environmentally benign nonmetal “green” oxidants [66][67][68][69][70][71][72][73]. For instance, iodosobenzene (PhIO) [74] has been widely used in many synthetic transformations. It was found that PhIO is efficient in realizing epoxidation of olefins [75

• generation of some unidentified byproducts. A solvent screening identified DMF to be the most appropriate solvent for this transformation (Table 1, entries 1–9). Other commonly employed oxidants, including phenyliodine(III) diacetate (PIDA), phenyliodine(III) bis(trifluoroacetate) (PIFA), and iodylbenzene

Thermal stability of N-heterocycle-stabilized iodanes – a systematic investigation

• Andreas Boelke,
• Yulia A. Vlasenko,
• Mekhman S. Yusubov,
• Boris J. Nachtsheim and
• Pavel S. Postnikov

Beilstein J. Org. Chem. 2019, 15, 2311–2318, doi:10.3762/bjoc.15.223

• stability with reactivity in a model oxygenation. Keywords: differential scanning calorimetry; hypervalent iodine; N-heterocycle; stability; thermogravimetry; Introduction Hypervalent iodine compounds, in particular aryl-λ3-iodanes, have found wide spread applications as oxidants and electrophilic group

• explosive properties of Togni’s reagent and very recently, Williams and co-workers analyzed the sensitivity of common oxidants including 2-iodoxybenzoic acid (IBX) and Dess–Martin periodinane (DMP) [19][20]. Waser and co-workers examined the thermal stability of the Zhdankin reagent ABX and compared it with

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

• different oxidation states, tolerance to various guiding groups, easy electroplating of C–H bonds, and the compatibility of many Pd(II) catalysts with oxidants make them act as ideal catalysts for C–H activations [34]. Over the last decade, a number of Pd-catalyzed methods have been developed to synthesize

Azologization and repurposing of a hetero-stilbene-based kinase inhibitor: towards the design of photoswitchable sirtuin inhibitors

• Christoph W. Grathwol,
• Nathalie Wössner,
• Sören Swyter,
• Adam C. Smith,
• Enrico Tapavicza,
• Robert K. Hofstetter,
• Anja Bodtke,
• Manfred Jung and
• Andreas Link

Beilstein J. Org. Chem. 2019, 15, 2170–2183, doi:10.3762/bjoc.15.214

• resemble a fixed (Z)-configuration of the stilbene double bond. Therefore, comparison with 2b could provide information concerning differential biological activity of the two photoisomers. By applying Mallory reaction conditions to a solution of 2b in methanol utilizing oxygen and iodine as oxidants we

α-Photooxygenation of chiral aldehydes with singlet oxygen

• Dominika J. Walaszek,
• Magdalena Jawiczuk,
• Jakub Durka,
• Olga Drapała and
• Dorota Gryko

Beilstein J. Org. Chem. 2019, 15, 2076–2084, doi:10.3762/bjoc.15.205

• methodologies enabling their functionalization, particularly in a stereoselective manner. Among them, asymmetric α-oxygenation of aldehydes still represents a challenging task. Most efficient methods require simultaneous use of chiral amines or Brønsted acids, and harsh oxidants like nitrosobenzene [1][2][3

Metal-free mechanochemical oxidations in Ertalyte^® jars

• Andrea Porcheddu,
• Francesco Delogu,
• Lidia De Luca,
• Claudia Fattuoni and
• Evelina Colacino

Beilstein J. Org. Chem. 2019, 15, 1786–1794, doi:10.3762/bjoc.15.172

• compounds under very mild conditions [6][7]. Initially used in a stoichiometric amount [8], over the last 20 years it has been exploited successfully in catalytic quantities in combination with other oxidants [9]. A diverse range of co-oxidant agents (N-chlorosuccinimide, NaOCl, Oxone®, PhIO, PhICl2, PhI

• such as the number (up to 15 balls, 5 mm Ø) and the diameter of balls (from 3 up to 10 mm Ø), or using a different base (KHCO3 or Na2CO3) turned out to be unsuccessful. The use of other solid oxidants such as trichloroisocyanuric acid (TCCA) did not bring any advantage to the process (Scheme 3), and

• sodium hypochlorite (NaOCl·5H2O) in the presence of a catalytic amount of a nitrosyl radical allowed developing a redox process without using any metal catalyst. With the aim to eliminate or at least reduce the use of solvents, NaOCl·5H2O, among all the oxidants tested, was the one that best fitted with

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

• greener oxidants [33]. During the writing of this review, we came across some reviews on IPs, however, their coverage is limited to the imidazo[1,2-a]pyridine nucleus deriving from either a particular starting material or to one type of reaction procedure (particularly C–H activation) with literature up

• , recyclable catalyst in the N-arylation of indoles [45][46]. Copper catalysts have shown exceptional enantioselectivity for reactions such as hydrosilylation, hydroboration, and heterogeneous as well as homogeneous hydrogenation [47][48][49]. Also, the copper salts found used as oxidants in a number of

Efficient synthesis of 4-substituted-ortho-phthalaldehyde analogues: toward the emergence of new building blocks

• Clémence Moitessier,
• Ahmad Rifai,
• Pierre-Edouard Danjou,
• Isabelle Mallard and
• Francine Cazier-Dennin

Beilstein J. Org. Chem. 2019, 15, 721–726, doi:10.3762/bjoc.15.67

• initiated in order to evaluate the stability of the protected RO-OPA and to certify the absence of OPA contamination [20]. Two major oxidants, SeO2 and DDQ were chosen for 5-methoxy and 5-acetoxy-4,5-dihydroisobenzofuran oxidation. As illustrated in Scheme 3, the reaction occurred with both reactants but

Selective benzylic C–H monooxygenation mediated by iodine oxides

• Kelsey B. LaMartina,
• Haley K. Kuck,
• Linda S. Oglesbee,
• Asma Al-Odaini and
• Nicholas C. Boaz

Beilstein J. Org. Chem. 2019, 15, 602–609, doi:10.3762/bjoc.15.55

• widely used in industrial processes as promoters of autoxidation in the functionalization of benzylic C–H bonds of aryl alkanes, such as in the synthesis of terephthalic acid from p-xylene [21]. Metal-free oxidants have been used in benzylic C–H to C–O functionalization. Specifically, the use of

• hypervalent iodine oxidants to mediate benzylic C–H oxidation is one area experiencing a surge of interest [22][23][24][25][26][27][28][29][30][31][32][33]. Nonmetal-based benzylic oxidations have also been mediated by species including, but not limited to, electron deficient quinones, photoexcited organic

• ) scaffold have been intensely studied for their ability to mediate hydrogen atom abstraction using a terminal oxidant of molecular oxygen [40][41][42][43][44][45]. NHPI has also been used in the effective C–H to C–O functionalization of benzylic positions using oxidants other than molecular oxygen including

Intramolecular cascade annulation triggered by rhodium(III)-catalyzed sequential C(sp²)–H activation and C(sp³)–H amination

• Liangliang Song,
• Guilong Tian,
• Johan Van der Eycken and
• Erik V. Van der Eycken

Beilstein J. Org. Chem. 2019, 15, 571–576, doi:10.3762/bjoc.15.52

• -catalyzed intramolecular annulation of alkyne-tethered hydroxamic esters for the synthesis of isoquinolones and pyridines without using external oxidants (Scheme 1a) [22]. Recently, we reported an intramolecular annulation of benzamides to synthesize indolizinones through RhIII-catalyzed C(sp2)–H activation

Tandem copper and photoredox catalysis in photocatalytic alkene difunctionalization reactions

• Nicholas L. Reed,
• Madeline I. Herman,
• Vladimir P. Miltchev and
• Tehshik P. Yoon

Beilstein J. Org. Chem. 2019, 15, 351–356, doi:10.3762/bjoc.15.30

• photocatalyst can be coupled to the reduction of Cu(I) to Cu(0), which can be observed precipitating from solution over the course of the reaction. Copper(II) salts have been demonstrated to be convenient terminal oxidants in a variety of synthetically useful catalytic reactions [23][24][25][26]. They are

• ) complex. We describe herein the results of this investigation, which has led to the identification of a tandem photoredox copper(II) catalytic system for the net-oxidative difunctionalization of alkenes. Results and Discussion A range of mild oxidants can oxidize copper(I) to copper(II), and the use of

• with ground-state dioxygen to afford unstable hydroperoxy radicals that can also decompose unproductively [32][33]. Indeed, in our previous study of photocatalytic alkene difunctionalization, we found that dioxygen and similar commonly used terminal oxidants resulted in unproductive decomposition of

Oxidative radical ring-opening/cyclization of cyclopropane derivatives

• Yu Liu,
• Qiao-Lin Wang,
• Zan Chen,
• Cong-Shan Zhou,
• Bi-Quan Xiong,
• Pan-Liang Zhang,
• Chang-An Yang and
• Quan Zhou

Beilstein J. Org. Chem. 2019, 15, 256–278, doi:10.3762/bjoc.15.23

• -opening, cyclization, oxidation and dehydrogenation and successfully furnished trifluoromethylthiolated 1,2-dihydronaphthalene derivatives 39 (Scheme 10) [67]. This reaction was achieved in the presence of 3.0 equiv of Na2S2O8 as the oxidants, 0.5 equiv of HMPA (N,N,N',N',N'',N

• nitrogen heterocyles 140 under acid-free conditions and used a well-defined catalyst [Ag(II)(bipy)2S2O8] at low loadings (Scheme 37) [117]. This finding indicated that the silver pyridine complex plays an important role in single electron oxidants of cyclopropanols. In the same year, a silver-catalyzed

Mn-mediated sequential three-component domino Knoevenagel/cyclization/Michael addition/oxidative cyclization reaction towards annulated imidazo[1,2-a]pyridines

• Olga A. Storozhenko,
• Alexey A. Festa,
• Delphine R. Bella Ndoutoume,
• Alexander V. Aksenov,
• Alexey V. Varlamov and
• Leonid G. Voskressensky

Beilstein J. Org. Chem. 2018, 14, 3078–3087, doi:10.3762/bjoc.14.287

• oxidative conditions has been developed. The employment of Mn(OAc)3·2H2O or KMnO4 as stoichiometric oxidants allowed the use of a wide range of nucleophiles, such as nitromethane, (aza)indoles, pyrroles, phenols, pyrazole, indazole and diethyl malonate. The formation of the target compounds presumably

• screening of the oxidants revealed, that the use of molecular iodine gave the desired product with 27% yield (Table 1, entry 4), while employment of NaOCl, NaIO4, MnO2, H2O2, or CuI/TBHP was not effective and led to the formation of complex mixtures (Table 1, entries 5–9), and use of CAN did not promote the

• conclusion, we have developed a practical route towards substituted chromenoimidazopyridines through a sequential three-component domino Knoevenagel/cyclization/Michael addition/oxidative cyclization reaction, employing cheap and abundant oxidants. The discovered process works in a broad substrate scope with

DABCO- and DBU-promoted one-pot reaction of N-sulfonyl ketimines with Morita–Baylis–Hillman carbonates: a sequential approach to (2-hydroxyaryl)nicotinate derivatives

• Soumitra Guin,
• Raman Gupta,
• Debashis Majee and
• Sampak Samanta

Beilstein J. Org. Chem. 2018, 14, 2771–2778, doi:10.3762/bjoc.14.254

• as the requirement of high temperatures or use of strong oxidants (H2O2, oxone, K2S2O8, TBHP, PIDA, NHPI etc.) that are not much compatible with functionality, precluding late-stage functionalization. Moreover, the scope of substitution on the pyridine ring is limited which in turn hampers the

Transition metal-free oxidative and deoxygenative C–H/C–Li cross-couplings of 2H-imidazole 1-oxides with carboranyl lithium as an efficient synthetic approach to azaheterocyclic carboranes

• Lidia A. Smyshliaeva,
• Mikhail V. Varaksin,
• Pavel A. Slepukhin,
• Oleg N. Chupakhin and
• Valery N. Charushin

Beilstein J. Org. Chem. 2018, 14, 2618–2626, doi:10.3762/bjoc.14.240

• reaction of 2,2-dimethyl-4-phenyl-2H-imidazole 1-oxide (1a) with carboranyllithium 2. The experiments performed have shown effects of the used oxidants, temperature regime, and exposure time after addition of an oxidant into the reaction mixture. As a result, the optimal conditions have been found to

A novel and practical asymmetric synthesis of eptazocine hydrobromide

• Ruipeng Li,
• Zhenren Liu,
• Liang Chen,
• Jing Pan,
• Kuaile Lin and
• Weicheng Zhou

Beilstein J. Org. Chem. 2018, 14, 2340–2347, doi:10.3762/bjoc.14.209

• , entry 3). When other oxidants, such as selenium oxide and manganese dioxide, were used, even at reflux temperature, no reaction took place (Table 2, entries 4 and 5). Owing to the concern of heavy metal pollution from the metal oxidant, organic oxidants were tested. Fortunately, DDQ in dioxane could

A general and atom-efficient continuous-flow approach to prepare amines, amides and imines via reactive N-chloramines

• Katherine E. Jolley,
• Michael R. Chapman and
• A. John Blacker

Beilstein J. Org. Chem. 2018, 14, 2220–2228, doi:10.3762/bjoc.14.196

• equivalents of aldehyde 17 led to 30% product formation (Table 3, entry 6). Notably, other oxidants such as H2O2 and NaOCl failed to produce any amide product. Likewise, attempts to couple morpholine in place of its N-chloro derivative reached only 19% conversion. Following the investigation of the batch

Hypervalent iodine compounds for anti-Markovnikov-type iodo-oxyimidation of vinylarenes

• Igor B. Krylov,
• Stanislav A. Paveliev,
• Mikhail A. Syroeshkin,
• Alexander A. Korlyukov,
• Pavel V. Dorovatovskii,
• Yan V. Zubavichus,
• Gennady I. Nikishin and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2018, 14, 2146–2155, doi:10.3762/bjoc.14.188

• the examined hypervalent iodine oxidants (PIDA, PIFA, IBX, DMP) PhI(OAc)2 proved to be the most effective; yields of iodo-oxyimides are 34–91%. A plausible reaction pathway includes the addition of an imide-N-oxyl radical to the double C=C bond and trapping of the resultant benzylic radical by iodine

• versatile leaving group for further transformations. The involvement of the iodine in the radical reactions of styrenes is complicated by the fact that unsaturated compounds readily undergo electrophilic iodination with the addition of an external nucleophile [61][62]. The oxidants used for the preparation

• %) was obtained using PhI(OAc)2 (Table 1, entry 2). Other iodine-based oxidants, such as PhI(OCOCF3)2 (Table 1, entry 10, yield 31%), IBX (Table 1, entries 11 and 12, yield 32–54%), DMP (Table 1, entries 13–14, yield 52%), showed less efficacy in this process. Peroxide oxidants, such as TBHP, TBAI/TBHP

Cobalt-catalyzed peri-selective alkoxylation of 1-naphthylamine derivatives

• Jiao-Na Han,
• Cong Du,
• Xinju Zhu,
• Zheng-Long Wang,
• Yue Zhu,
• Zhao-Yang Chu,
• Jun-Long Niu and
• Mao-Ping Song

Beilstein J. Org. Chem. 2018, 14, 2090–2097, doi:10.3762/bjoc.14.183

• effective and the alkoxylated product 3aa could be isolated in 82% yield. Next, the effect of oxidants on the reactivity was investigated, and Ag2CO3 showed a superior result compared with alternative oxidants (Table 1, entries 6–8). Moreover, DCE and HFIP as co-solvents demonstrated higher reactivity

Applications of organocatalysed visible-light photoredox reactions for medicinal chemistry

• Michael K. Bogdos,
• Emmanuel Pinard and
• John A. Murphy

Beilstein J. Org. Chem. 2018, 14, 2035–2064, doi:10.3762/bjoc.14.179

• oxidants are employed. For example, the oxidation of alcohols to carbonyls traditionally requires strong oxidants (Cr(VI) species, IBX, DMP), whereas similar reactions using photochemical methods can utilise oxygen (O2) as the oxidising agent. The oxidising agent can accept electrons either from the