Disposable cartridge concept for the on-demand synthesis of turbo Grignards, Knochel–Hauser amides, and magnesium alkoxides

• Mateo Berton,
• Kevin Sheehan,
• Andrea Adamo and
• D. Tyler McQuade

Beilstein J. Org. Chem. 2020, 16, 1343–1356, doi:10.3762/bjoc.16.115

• ⋅LiCl solution, in the collection flask, away from a heat source. System scope: Bis(trimethylsilyl)amine (HMDS), diphenylamine (Ph2NH), aniline (PhNH2), and 2,2,6,6-tetramethylpiperidine (TMPH) were selected as substrates. Ph2NH, HMDS, and PhNH2 due to their lower pKa (25, 30, and 31, respectively, in

Distinctive reactivity of N-benzylidene-[1,1'-biphenyl]-2-amines under photoredox conditions

• Shrikant D. Tambe,
• Kwan Hong Min,
• Naeem Iqbal and
• Eun Jin Cho

Beilstein J. Org. Chem. 2020, 16, 1335–1342, doi:10.3762/bjoc.16.114

• unprecedented reductive coupling of N-benzylidene-[1,1'-biphenyl]-2-amines with an aliphatic amine. The presence of a phenyl substituent in the aniline moiety of the substrate was critical for the reactivity. The reaction proceeded via radical–radical cross-coupling of α-amino radicals generated by proton

• photocatalytic synthetic methods are mainly limited to aniline-based substrates and do not encompass aliphatic amines. We planned the synthesis of 1,2-diamine compounds having an aliphatic amine moiety by the intermolecular coupling of N-benzylidines with aliphatic amines that not only act as coupling partner

• 2p), did not have any significant impact on the reaction outcome. The heteroaryl ring-bearing substrates (2n and 2o) also underwent the transformation, and furnished the valuable vicinal diamine products. The modifications on the aniline moiety were also suitable, and substrates with both electron

The charge-assisted hydrogen-bonded organic framework (CAHOF) self-assembled from the conjugated acid of tetrakis(4-aminophenyl)methane and 2,6-naphthalenedisulfonate as a new class of recyclable Brønsted acid catalysts

• Svetlana A. Kuznetsova,
• Alexander S. Gak,
• Yulia V. Nelyubina,
• Vladimir A. Larionov,
• Han Li,
• Michael North,
• Vladimir P. Zhereb,
• Alexander F. Smol'yakov,
• Artem O. Dmitrienko,
• Michael G. Medvedev,
• Igor S. Gerasimov,
• Ashot S. Saghyan and
• Yuri N. Belokon

Beilstein J. Org. Chem. 2020, 16, 1124–1134, doi:10.3762/bjoc.16.99

• crystals (Figure 5) reached a plateau at 160 °C after 5.9% of the mass was removed as water. The plateau was maintained until 340 °C, when the sample underwent an endothermic decomposition. The decomposition produced sulfur dioxide, naphthalene, and aniline, according to the infrared spectra of the

• Brønsted acid catalyst) cation exchange resin IR-120, which contains sulfonic acid functionalities, was mixed in its hydrogen form with aniline to give a model of F-1. An attempted use of the resulting compound with the same amount of ammonium groups as in F-1 for the conversion of the epoxide 2 into the

Accelerating fragment-based library generation by coupling high-performance photoreactors with benchtop analysis

• Quentin Lefebvre,
• Christophe Salomé and
• Thomas C. Fessard

Beilstein J. Org. Chem. 2020, 16, 982–988, doi:10.3762/bjoc.16.87

• electrochemically-mediated nickel-catalyzed cross-couplings. Electron-deficient aniline products are less prone to oxidative decomposition. BCP-amines were viable coupling partners but gave the corresponding products 1a–e in poor purities. Simple azetidines partook the reaction to give 2a–c while azaspiro[3,3

Recent advances in Cu-catalyzed C(sp³)–Si and C(sp³)–B bond formation

• Balaram S. Takale,
• Ruchita R. Thakore,
• Elham Etemadi-Davan and
• Bruce H. Lipshutz

Beilstein J. Org. Chem. 2020, 16, 691–737, doi:10.3762/bjoc.16.67

• significantly. However, with the aniline derivative 69 (R = Ph on nitrogen), the ee dropped precipitously (Scheme 15). Chen et al. used a paracyclophane-based NHC ligand, along with Cu2O, to perform similar asymmetric 1,2-silyl additions onto activated imines. For several substrates (47) studied, the chemical

Microwave-assisted efficient and facile synthesis of tetramic acid derivatives via a one-pot post-Ugi cascade reaction

• Yong Li,
• Zheng Huang,
• Jia Xu,
• Yong Ding,
• Dian-Yong Tang,
• Jie Lei,
• Hong-yu Li,
• Zhong-Zhu Chen and
• Zhi-Gang Xu

Beilstein J. Org. Chem. 2020, 16, 663–669, doi:10.3762/bjoc.16.63

• tetramic acid derivatives with potential interesting biological activities via an Ugi/Dieckmann cyclization strategy. Results and Discussion We initially stirred a mixture of ethyl glyoxylate (1a), aniline (2a), 2-(4-chlorophenyl)acetic acid (3a), and benzylisonitrile (4a) in methanol at room temperature

Preparation and in situ use of unstable N-alkyl α-diazo-γ-butyrolactams in Rh^II-catalyzed X–H insertion reactions

• Maria Eremeyeva,
• Daniil Zhukovsky,
• Dmitry Dar’in and
• Mikhail Krasavin

Beilstein J. Org. Chem. 2020, 16, 607–610, doi:10.3762/bjoc.16.55

• , that we observed with 2,6-dimethylaniline. With this unreactive, sterically hindered aromatic amine, 6c is likely to undergo either the unwanted N2→O oxidation or dimerize to bishydrazone 5, whereupon the resulting intermediate would be eventually trapped by the aniline to give 8b (Scheme 2). The

Recent advances in photocatalyzed reactions using well-defined copper(I) complexes

• Mingbing Zhong,
• Xavier Pannecoucke,
• Philippe Jubault and
• Thomas Poisson

Beilstein J. Org. Chem. 2020, 16, 451–481, doi:10.3762/bjoc.16.42

• under air, N,N-dialkylated aniline derivatives were reacted with various N-substituted maleimides and benzylidenemalonitrile to provide polysubstituted tetrahydroquinolines in moderate to good yields. When N-aryltetrahydroisoquinoline was used instead of N,N-dialkylated anilines, octahydroisoquinolo[2,1

• -a]pyrrolo[3,4-c]quinoline derivatives were obtained for the first time. This transformation starts with the oxidation of the excited photocatalyst with O2. The aniline is then oxidized into an N-centered radical cation, which further gives the α-amino radical. The latter reacts with the maleimide to

Photophysics and photochemistry of NIR absorbers derived from cyanines: key to new technologies based on chemistry 4.0

• Bernd Strehmel,
• Christian Schmitz,
• Ceren Kütahya,
• Yulian Pang,
• Anke Drewitz and
• Heinz Mustroph

Beilstein J. Org. Chem. 2020, 16, 415–444, doi:10.3762/bjoc.16.40

• patterns. Moreover, synthesis of pentamethine cyanines II follows a route requesting cb (Scheme 4) as precursor. There serve some aldehydes as source to synthesize this precursor by reaction with aniline. Similar reaction philosophy also follows synthesis of cb-0 (Scheme 4) to synthesize open heptamethines

Architecture and synthesis of P,N-heterocyclic phosphine ligands

• Wisdom A. Munzeiwa,
• Bernard Omondi and
• Vincent O. Nyamori

Beilstein J. Org. Chem. 2020, 16, 362–383, doi:10.3762/bjoc.16.35

• phosphorus can be adjusted by changing the bulkiness of substituents around both, the N and P centers [99]. When reacting anilines and chlorophosphines under basic conditions they undergo P–N bond formation affording conventional aminophosphines [100][101]. A facile alternative method replaces the aniline

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

• , the reaction is initiate with the excitation of the photocatalyst, which further oxidizes the aniline derivative 106 to generate the arene radical cation 108. Then, the intermediate 109 is formed by deprotonation, which, upon reaction with a nitrate radical, gives the desired product 107. Aryl C–H

• catalyst. Proposed mechanism for the trifluoromethylation of 88. Plausible mechanism for the synthesis of substituted coumarins. Mechanism proposed for the phosphonylation reaction of 100. Plausible mechanism for the nitration of aniline derivatives via photoredox catalysis. Proposed mechanism for the

Combination of multicomponent KA² and Pauson–Khand reactions: short synthesis of spirocyclic pyrrolocyclopentenones

• Riccardo Innocenti,
• Elena Lenci,
• Gloria Menchi and
• Andrea Trabocchi

Beilstein J. Org. Chem. 2020, 16, 200–211, doi:10.3762/bjoc.16.23

• the equatorial alcohol, although in lower yield. The use of CeCl3 together with EtMgBr was found particularly effective to suppress conjugate additions, with similar yield as reported for analogous substrates [56]. Subsequent acid-catalyzed displacement of the hydroxy moiety with aniline in the

Starazo triple switches – synthesis of unsymmetrical 1,3,5-tris(arylazo)benzenes

• Andreas H. Heindl and
• Hermann A. Wegner

Beilstein J. Org. Chem. 2020, 16, 22–31, doi:10.3762/bjoc.16.4

• using an aqueous ammonium sulfide solution to furnish aniline 6 in 65% yield [20]. After oxidation of 6 to its nitroso analogue 7 [21], a Baeyer–Mills reaction with aniline yielded the targeted azobenzene building block 8 in 87% yield (i.e., 53% yield over four steps). After the successful synthesis of

Chemical tuning of photoswitchable azobenzenes: a photopharmacological case study using nicotinic transmission

• Lorenzo Sansalone,
• Jun Zhao,
• Matthew T. Richers and
• Graham C. R. Ellis-Davies

Beilstein J. Org. Chem. 2019, 15, 2812–2821, doi:10.3762/bjoc.15.274

• catalytic hydrogenation to 4 followed by protection with TBDMS to give 5 in 63% yield for three steps. The synthesis of the other half of the photochrome started with bromination of difluorinated aniline to give 6 followed by copper-catalyzed cyanation to 7 in 62% overall yield. Diazonization of 7 with

Photoreversible stretching of a BAPTA chelator marshalling Ca²⁺-binding in aqueous media

• Aurélien Ducrot,
• Arnaud Tron,
• Robin Bofinger,
• Ingrid Sanz Beguer,
• Jean-Luc Pozzo and
• Nathan D. McClenaghan

Beilstein J. Org. Chem. 2019, 15, 2801–2811, doi:10.3762/bjoc.15.273

• over Mg2+ ions, and relative insensitivity to pH in biological media due to the relatively low pKa of the electron-poor aniline nitrogens [1]. BAPTA-type molecules complex Ca2+ in an octacoordinated fashion, involving the two aniline functions, the two central ether oxygens and the four carboxylates

• then underwent a regioselective monodeprotection to generate a lone phenol group. The phenolate was reacted with 1,2-dibromoethane and the nitrobenzene groups were reduced to the corresponding anilines giving 1a. The double aniline 1a was alkylated using ethyl bromoacetate under basic conditions in

• noted: N–Ca2+: 2.35 and 2.49 Å cf. 3.24 and 3.03 Å. Smaller differences were noted considering the COO−–Ca2+: 2.20, 2.19, 2.29 and 2.70 Å cf. 2.21, 2.21, 2.23 and 2.23 Å or the ether linkage O–Ca2+: 2.44 and 2.49 Å cf. 2.46 and 2.51 Å. Most significantly, the aniline N–N distance is stretched from 4.71

Emission solvatochromic, solid-state and aggregation-induced emissive α-pyrones and emission-tuneable 1H-pyridines by Michael addition–cyclocondensation sequences

• Natascha Breuer,
• Irina Gruber,
• Christoph Janiak and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2019, 15, 2684–2703, doi:10.3762/bjoc.15.262

• ), phenylacetylene (2a), and ethyl cyanoacetate (4) within the AMAC sequence (Scheme 2). Surprisingly, the desired α-pyrone was not isolated, but two other compounds were detected. On the one hand a 1H-pyridine derivative 5a (2% yield) and on the other hand an aniline derivative with two ester groups (4% yield

• be isolated in 30% yield, while the aniline derivative was not formed (Scheme 3). There are only a few known methods for the synthesis of this kind of 1H-pyridines. In a cyclocondensation, starting from 1,3-dicarbonyl compounds, Elnagdi and co-workers synthesized 1H-pyridines with an additional cyano

• -pyrones from acid chlorides, terminal alkynes and dialkyl malonates. Consecutive pseudo-four-component alkynylation–Michael addition–cyclocondensation (AMAC) synthesis of 1H-pyridines 5a and an aniline derivative. Consecutive pseudo-four-component alkynylation–Michael addition–cyclocondensation (AMAC

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

• employed methods: synthesis of the phenyl-substituted silicon rhodamine 22 by Suzuki cross coupling affords the product in a similar yield compared to the addition of phenyllithium to xanthone 12 or the attack of the double metallated bis-aniline 4 (R1 = R2 = Me, M = Mg) to the benzoic acid methyl ester

α,ß-Didehydrosuberoylanilide hydroxamic acid (DDSAHA) as precursor and possible analogue of the anticancer drug SAHA

• Shital K. Chattopadhyay,
• Subhankar Ghosh,
• Sarita Sarkar and
• Kakali Bhadra

Beilstein J. Org. Chem. 2019, 15, 2524–2533, doi:10.3762/bjoc.15.245

• derivative [21]. Thus, anilide 7a was prepared by straightforward amide bond formation between aniline and 6-heptenoic acid (5) to study its cross metathesis with the hydroxamate 8. Pleasingly, use of Grubbs’ second generation catalyst [(1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro

• of comparable magnitude or even better than SAHA [23]. We therefore prepared the one-carbon shorter dehydro-SAHA derivative 11g starting from aniline and 5-hexenoic acid (6) following the three-step sequence. Compound 11g displayed similar spectroscopic behaviour to that of SAHA. In an alternative

• approach, cross metathesis of 8 was first done with methyl heptenoate to prepare compound 12 in good yield. This was then hydrolyzed to get the corresponding acid 13. An amide bond formation between this acid and aniline under usual conditions provided DDSAHA derivative 10a in an overall yield of 56% over

A toolbox of molecular photoswitches to modulate the CXCR3 chemokine receptor with light

• Xavier Gómez-Santacana,
• Sabrina M. de Munnik,
• Tamara A. M. Mocking,
• Niels J. Hauwert,
• Shanliang Sun,
• Prashanna Vijayachandran,
• Iwan J. P. de Esch,
• Henry F. Vischer,
• Maikel Wijtmans and
• Rob Leurs

Beilstein J. Org. Chem. 2019, 15, 2509–2523, doi:10.3762/bjoc.15.244

• -nitrobenzaldehyde (8a) to give the corresponding tertiary amine 9a in high yield. The nitro group of 9a was subsequently reduced by SnCl2 in high yield. The resulting aniline 10a was used to obtain the azo compounds 12a–e in varying yields through a Mills reaction with the corresponding nitroso compounds 11a–e

• overall yields similar to the ones obtained for 2a–e. However, 2-iodonitrosobenzene cannot be accessed through oxidation of the corresponding aniline owing to oxidation sensitivity of the iodine atom. Therefore, an alternative route had to be used to synthesize 3f–h (Scheme 2). The route began with the

• compound 9c which was reduced to aniline 10c and used to obtain the azo compounds 14a–d,f–i in variable yields through a Mills reaction with the corresponding nitroso compounds 11a-b,e–j. Methylation of 14a–d,f–i with MeI yielded compounds 4a–d,f–g,i as orange powders with ≥99% trans-isomer in moderate to

Photochromic diarylethene ligands featuring 2-(imidazol-2-yl)pyridine coordination site and their iron(II) complexes

• Andrey G. Lvov,
• Max Mörtel,
• Anton V. Yadykov,
• Frank W. Heinemann,
• Valerii Z. Shirinian and
• Marat M. Khusniyarov

Beilstein J. Org. Chem. 2019, 15, 2428–2437, doi:10.3762/bjoc.15.235

• condensation [33] of 3-(hydroxyimino)pentane-2,4-dione, aniline, and 2-pyridinecarboxaldehyde (Scheme 1). The structure of 1 was confirmed by X-ray crystallography [34]. The ketone 1 was subsequently used for the synthesis of desired photochromic ligands with cyclopentenone (3), cyclopentene (4), and

Small anion-assisted electrochemical potential splitting in a new series of bistriarylamine derivatives: organic mixed valency across a urea bridge and zwitterionization

• Keishiro Tahara,
• Tetsufumi Nakakita,
• Alyona A. Starikova,
• Takashi Ikeda,
• Masaaki Abe and
• Jun-ichi Kikuchi

Beilstein J. Org. Chem. 2019, 15, 2277–2286, doi:10.3762/bjoc.15.220

• ’’-dimethyltriphenylamine by NMR [62] and used in the next step without further purification. To a solution of triphosgene (0.296 g, 1.00 mmol) in 15 mL of dry dichloromethane at 0 °C a solution of aniline (0.093 g, 1.00 mmol) and 0.56 mL of triethylamine in dry dichloromethane (15 mL) was added. After 10 min of stirring

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

Tautomerism as primary signaling mechanism in metal sensing: the case of amide group

• Vera Deneva,
• Georgi Dobrikov,
• Aurelien Crochet,
• Daniela Nedeltcheva,
• Katharina M. Fromm and
• Liudmil Antonov

Beilstein J. Org. Chem. 2019, 15, 1898–1906, doi:10.3762/bjoc.15.185

• solution: Aniline (0.90 mL, 10.00 mmol) was dissolved in a mixture of concentrated hydrochloric acid (5 mL) and distilled water (20 mL). A solution of sodium nitrite (0.83 g, 12.00 mmol) in distilled water (5 mL) was prepared in a test tube. The sodium nitrite solution was added dropwise to the acidic

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

• the past few years [57]. Recently, Buchwald and Castillo have reviewed the exceptional utility of Pd-catalyzed C–N cross-coupling reactions for the preparation of anilines and aniline derivatives [58]. In many of the reactions, palladium was used along with a co-catalyst to enhance its catalytic

Enantioselective PCCP Brønsted acid-catalyzed aza-Piancatelli rearrangement

• Gabrielle R. Hammersley,
• Meghan F. Nichol,
• Helena C. Steffens,
• Jose M. Delgado,
• Gesine K. Veits and
• Javier Read de Alaniz

Beilstein J. Org. Chem. 2019, 15, 1569–1574, doi:10.3762/bjoc.15.160

• -, meta-, and para-substituted aniline derivatives. The reaction of anilines bearing an electron-withdrawing group at the para-position afforded the optimal balance between efficiency and enantioselectivity. Consistent with Rueping’s work [35], ortho-aminobenzoic acid, which contains an additional

• bonding capability of the carboxylic acid group. In contrast, with the exception of 7p and 7q, a lower yield was obtained when ortho-aminobenzoic acid was used. Presumably, this decrease in efficiency is due to the increased steric bulk on the aniline, which slows the initial nucleophilic attack on the

• acid catalyzed reaction shows good substrate scope and proceeds well with a range of aniline and furylcarbinol derivatives. The ability to control the absolute stereochemistry of the 4π electrocylization using an inexpensive and easy to prepare chiral Brønsted acid catalyst holds tremendous promise for