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

• of promising heterocyclic carboranes: (i) condensation of decaborane (B10H14) with substituted acetylenes [27][28][29][30], (ii) carboryne-based cycloaddition reactions [31][32][33], and (iii) C–X/C–M cross coupling of halogenated azaheterocycles (X = Br, Cl, F) with carborane organometallic

Learning from B₁₂ enzymes: biomimetic and bioinspired catalysts for eco-friendly organic synthesis

• Keishiro Tahara,
• Ling Pan,
• Toshikazu Ono and
• Yoshio Hisaeda

Beilstein J. Org. Chem. 2018, 14, 2553–2567, doi:10.3762/bjoc.14.232

• methylcobalamin and adenosylcobalamin (coenzyme B12) that serve as organometallic cofactors in B12-dependent enzymes. The photolysis (thermolysis) of alkylcob(III)alamins leads to the formation of the corresponding alkyl radical and cob(II)alamin with homolytic Co(III)–C bond cleavage (Figure 1b). This high

• functions of B12 are exploited by bound apoenzymes. B12 is recycled or reactivated in vivo as observed in methyonine synthetases. Understanding the mechanisms of B12 enzyme reactions and the role of B12 is very important from the viewpoint of bioinorganic and organometallic chemistry, organic syntheses, and

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

• (SM) cross-coupling reaction is also considered as one of the most versatile methods for C–C bond formation [8][9][10][11][12]. Application of a wide range of organometallic reagents (e.g., organoboron reagents) are possible due to their commercial availability. Owing to the mild reaction conditions

Efficient catalytic alkyne metathesis with a fluoroalkoxy-supported ditungsten(III) complex

• Henrike Ehrhorn,
• Janin Schlösser,
• Dirk Bockfeld and
• Matthias Tamm

Beilstein J. Org. Chem. 2018, 14, 2425–2434, doi:10.3762/bjoc.14.220

• , MMPO = 1-methoxy-2-methylpropan-2-ol) was isolated which catalyzed alkyne metathesis of 1-heptyne at elevated temperatures [68] and to date represents the only well-defined ditungsten complex which has been successfully used in alkyne metathesis. The organometallic chemistry of the M2X6 complexes (X

A challenging redox neutral Cp*Co(III)-catalysed alkylation of acetanilides with 3-buten-2-one: synthesis and key insights into the mechanism through DFT calculations

• Andrew Kenny,
• Alba Pisarello,
• Arron Bird,
• Paula G. Chirila,
• Alex Hamilton and
• Christopher J. Whiteoak

Beilstein J. Org. Chem. 2018, 14, 2366–2374, doi:10.3762/bjoc.14.212

• ketone oxygen to form Int 1. This allows for reasonably close proximity of the Csp²-H proton for internal abstraction by the acetate group. The C–H activation step has an energy span barrier of 17.8 kcal mol−1, leading to the formation of the 6-membered organometallic cobaltacycle (Int 2AcOH) with an

• in molecules (QTAIM) analysis using Multiwfn software [28] of the two intermediate structures, identifying the relevant parameters at the bond critical points (bcp) of interest. QTAIM analysis has been used previously in the field of transition metal organometallic complexes to understand ligand

• benzamide example, the key step of co-ordination of the unsaturated coupling partner to the organometallic intermediate is significantly less favourable, thus a number of resting states of the catalyst become energetically more accessible, providing the reason for the requirement of more forcing conditions

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

• the unwanted isomer [3][4][5][6]. Other asymmetric syntheses of 1 have been reported in the literature. These relied either on organometallic catalysis [7], asymmetric tandem addition to chiral tetrahydronaphthalenes [8], bioenzymatic steps [9] or diastereoselective Evans alkylation from oxazolidinone

Bi-mediated allylation of aldehydes in [bmim][Br]: a mechanistic investigation

• Mrunesh Koli,
• Sucheta Chatterjee,
• Subrata Chattopadhyay and
• Dibakar Goswami

Beilstein J. Org. Chem. 2018, 14, 2198–2203, doi:10.3762/bjoc.14.193

• reaction. In other RTILs, the reaction was either not proceeding at all, or was very sluggish. The specific advantages provided by [bmim][Br] prompted us for further mechanistic studies as discussed below. Mechanistic studies For this, we first probed the nature of the organometallic species responsible

Evaluation of dispersion type metal···π arene interaction in arylbismuth compounds – an experimental and theoretical study

• Ana-Maria Preda,
• Małgorzata Krasowska,
• Lydia Wrobel,
• Philipp Kitschke,
• Phil C. Andrews,
• Jonathan G. MacLellan,
• Lutz Mertens,
• Marcus Korb,
• Tobias Rüffer,
• Heinrich Lang,
• Alexander A. Auer and
• Michael Mehring

Beilstein J. Org. Chem. 2018, 14, 2125–2145, doi:10.3762/bjoc.14.187

• ]. With regard to this the high relevance of London dispersion type interactions in molecular organometallic chemistry was recently summarized by Liptrot and Power [9]. It should be noted that in this context and more generally organometallic bismuth compounds are witnessing growing attention since

• applications in the field of supramolecular chemistry [10][11][12] and pharmacology are of interest [13][14][15]. Lately, several studies regarding the metal···π interactions in organometallic compounds of antimony and bismuth [16][17][18][19] have been reported including intramolecular [20][21][22] and

• dispersion type interactions including bismuth···π interaction in the solid state. This prompted us to have a closer look at these simple organometallic compounds. Noteworthy, the first report on the synthesis of Ph3Bi dates back to 1887, which was based on the reaction of sodium alloy and bromobenzene [46

Coordination-driven self-assembly vs dynamic covalent chemistry: versatile methods for the synthesis of molecular metallarectangles

• Li-Li Ma,
• Jia-Qin Han,
• Wei-Guo Jia and
• Ying-Feng Han

Beilstein J. Org. Chem. 2018, 14, 2027–2034, doi:10.3762/bjoc.14.178

• desired tetranuclear metallarectangles were synthesized by using coordination-driven self-assembly of half-sandwich rhodium-based organometallic clip units and organic ligands. The reaction of such an organometallic clip with 4-formylpyridine provided a dinuclear molecular tweezer with pendant aldehyde

• groups, and subsequent [4 + 4] condensation reactions with diamines provides another route to the target metallarectangles in good yields. The same assemblies can also be easily isolated in one-pot procedures by mixing the organometallic clip, diamines and 4-formylpyridine. Keywords: coordination-driven

• self-assembly; dynamic covalent chemistry; half-sandwich rhodium complex; metallarectangles; one-pot reaction; supramolecular chemistry; Introduction Over the past two decades, supramolecular structures with organometallic half-sandwich fragments have attracted much attention, including

Recent advances in materials for organic light emitting diodes

• Eli Zysman-Colman

Beilstein J. Org. Chem. 2018, 14, 1944–1945, doi:10.3762/bjoc.14.168

• in design, from fluorescent compounds to phosphorescent organometallic complexes to organic thermally activated delayed fluorescence (TADF) molecules, the latter driving tremendous recent excitement within the field of organic semiconductor research. This thematic issue of the Beilstein Journal of

Recent advances in hypervalent iodine(III)-catalyzed functionalization of alkenes

• Xiang Li,
• Pinhong Chen and
• Guosheng Liu

Beilstein J. Org. Chem. 2018, 14, 1813–1825, doi:10.3762/bjoc.14.154

• Xiang Li Pinhong Chen Guosheng Liu State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China 10.3762/bjoc.14.154 Abstract Hypervalent iodine(III

Thiocarbonyl-enabled ferrocene C–H nitrogenation by cobalt(III) catalysis: thermal and mechanochemical

• Santhivardhana Reddy Yetra,
• Zhigao Shen,
• Hui Wang and
• Lutz Ackermann

Beilstein J. Org. Chem. 2018, 14, 1546–1553, doi:10.3762/bjoc.14.131

• by weakly-coordinating thiocarbonyl-assisted cobalt catalysis. Thus, carboxylates enabled ferrocene C–H nitrogenations with dioxazolones, featuring ample substrate scope and robust functional group tolerance. Mechanistic studies provided strong support for a facile organometallic C–H activation

• to a significant H/D scrambling in proximity to the thiocarbonyl group. These findings are indicative of a reversible, thus facile organometallic C–H cobaltation regime (Scheme 4). Next, intermolecular competition experiments revealed that electron-rich arylated thiocarbonylferrocene 1 reacted

Recent advances in phosphorescent platinum complexes for organic light-emitting diodes

• Cristina Cebrián and
• Matteo Mauro

Beilstein J. Org. Chem. 2018, 14, 1459–1481, doi:10.3762/bjoc.14.124

• organometallic compounds based on heavy transition metal complexes (TMCs) are an appealing research topic of enormous current interest. Amongst all different fields in which they found valuable application, development of emitting materials based on TMCs have become crucial for electroluminescent devices such as

Three-component coupling of aryl iodides, allenes, and aldehydes catalyzed by a Co/Cr-hybrid catalyst

• Kimihiro Komeyama,
• Shunsuke Sakiyama,
• Kento Iwashita,
• Itaru Osaka and
• Ken Takaki

Beilstein J. Org. Chem. 2018, 14, 1413–1420, doi:10.3762/bjoc.14.118

• , leading to multi-substituted carbon frameworks (Scheme 1, bottom) [2][3]. The nucleophilic and π-electrophilic organometallic intermediates are used properly in their favorable circumstances. Transmetalation is one of the most vital elemental processes used to drastically change the reactivity of

Enhanced quantum yields by sterically demanding aryl-substituted β-diketonate ancillary ligands

• Rebecca Pittkowski and
• Thomas Strassner

Beilstein J. Org. Chem. 2018, 14, 664–671, doi:10.3762/bjoc.14.54

• Rebecca Pittkowski Thomas Strassner Physical Organic Chemistry, Technische Universität Dresden, Bergstraße, 01069 Dresden, Germany 10.3762/bjoc.14.54 Abstract Luminescent organometallic platinum(II) compounds are of interest as phosphors for organic light emitting devices. Their emissive

• emission properties of organometallic complexes can be tuned by employing different ligand structures. For platinum(II) complexes, the influence of both cyclometalating [21][22][23][24][25][26] and auxiliary ligand [27][28][29][30][31][32] on the emission color as well as their efficiency has been

Nucleophilic fluoroalkylation/cyclization route to fluorinated phthalides

• Masanori Inaba,
• Tatsuya Sakai,
• Shun Shinada,
• Tsuyuka Sugiishi,
• Yuta Nishina,
• Norio Shibata and
• Hideki Amii

Beilstein J. Org. Chem. 2018, 14, 182–186, doi:10.3762/bjoc.14.12

• nucleophilic trifluoromethylation of acid anhydrides to produce γ-hydroxy-γ-trifluoromethyl-γ-butyrolactones, which acted as good precursors in the synthesis of γ-trifluoromethyl-γ-butyrolactones with organometallic reagents [16]. All these protocols involve multiple steps to obtain trifluoromethylphthalides

Gram-scale preparation of negative-type liquid crystals with a CF₂CF₂-carbocycle unit via an improved short-step synthetic protocol

• Tatsuya Kumon,
• Shohei Hashishita,
• Takumi Kida,
• Shigeyuki Yamada,
• Takashi Ishihara and
• Tsutomu Konno

Beilstein J. Org. Chem. 2018, 14, 148–154, doi:10.3762/bjoc.14.10

• . The tetrafluorinated multicyclic molecules were successfully obtained in only five or six reaction steps without the need for special handling techniques, as is generally required for thermally unstable organometallic species, representing a reduction of three reaction steps. The improved short-step

Aminomethylation/hydrogenolysis as an alternative to direct methylation of metalated isoquinolines – a novel total synthesis of the alkaloid 7-hydroxy-6-methoxy-1-methylisoquinoline

• Benedikt C. Melzer,
• Jan G. Felber and
• Franz Bracher

Beilstein J. Org. Chem. 2018, 14, 130–134, doi:10.3762/bjoc.14.8

• with methylmagnesium bromide [17], and direct methylation using radical reactions [9][18][19]. Hence, we searched for a more viable method for the introduction of the methyl group. A prerequisite was that the organometallic intermediate should be trapped by an electrophile which could later be

Recent applications of click chemistry for the functionalization of gold nanoparticles and their conversion to glyco-gold nanoparticles

• Vivek Poonthiyil,
• Thisbe K. Lindhorst,
• Vladimir B. Golovko and
• Antony J. Fairbanks

Beilstein J. Org. Chem. 2018, 14, 11–24, doi:10.3762/bjoc.14.2

• (Scheme 9). Astruc and co-workers have also reported that the use of copper(I) (hexabenzyl)tris(2-aminoethyl)amine bromide ([Cu(I)tren(CH2Ph6)]Br) instead of the CuSO4–ascorbic acid system improves the efficiency of CuAAC for the functionalization of AuNPs with a wide variety of organic, organometallic

Reactivity of bromoselenophenes in palladium-catalyzed direct arylations

• Aymen Skhiri,
• Ridha Ben Salem,
• Jean-François Soulé and
• Henri Doucet

Beilstein J. Org. Chem. 2017, 13, 2862–2868, doi:10.3762/bjoc.13.278

• ][5][6][7][8][9], Suzuki [10][11][12][13][14][15][16][17][18][19], or Kumada [20] couplings [21] (Scheme 1a and b). However, all these procedures require the preparation of an organometallic or a boron derivative of one of the coupling partners, and provide an organometallic salt (MX) as waste. In

The photodecarboxylative addition of carboxylates to phthalimides as a key-step in the synthesis of biologically active 3-arylmethylene-2,3-dihydro-1H-isoindolin-1-ones

• Ommid Anamimoghadam,
• Saira Mumtaz,
• Anke Nietsch,
• Gaetano Saya,
• Cherie A. Motti,
• Jun Wang,
• Peter C. Junk,
• Ashfaq Mahmood Qureshi and
• Michael Oelgemöller

Beilstein J. Org. Chem. 2017, 13, 2833–2841, doi:10.3762/bjoc.13.275

• compound 4, originating from intramolecular nucleophilic substitution, was obtained as a byproduct in 25–30%. Noteworthy, compound 4 is formed as the only product when 1a is treated with organometallic reagents [48][49][50]. When the photoreaction was repeated in a 1:1 mixture of acetone and pH 7 buffer at

• bond formation (path A), as postulated by Griesbeck et al. for the photocyclization of phthaloyl-L-methionine [58]. Alternatively, the alcoholate obtained after C–C bond formation may cyclize to the oxazolidine (path B), as known from reactions of 1a with organometallic reagents [48][49][50]. When

Asymmetric synthesis of propargylamines as amino acid surrogates in peptidomimetics

• Matthias Wünsch,
• David Schröder,
• Tanja Fröhr,
• Lisa Teichmann,
• Sebastian Hedwig,
• Nils Janson,
• Clara Belu,
• Jasmin Simon,
• Shari Heidemeyer,
• Philipp Holtkamp,
• Jens Rudlof,
• Lennard Klemme,
• Alessa Hinzmann,
• Beate Neumann,
• Hans-Georg Stammler and
• Norbert Sewald

Beilstein J. Org. Chem. 2017, 13, 2428–2441, doi:10.3762/bjoc.13.240

• propargylamines by nucleophilic addition. The synthesis of propargylamines by diastereoselective reductive amination requires alkynyl ketones, which are difficult to prepare and are unstable towards reductive conditions. In approach I, organometallic nucleophiles are added to N-sulfinyl propargylimines, derived

• from aldehydes. According to approach II, a metallated terminal alkyne is added to an N-sulfinylaldimine. In approach I, the organometallic nucleophile is transferring the amino acid side chain, in approach II, the amino acid side chain comes from the aldehyde incorporated in the imine. Results and

• -butyl sulfinamide led to the enantiomerically pure sulfinylimines 3a and 3b, which were reacted with a variety of organometallic compounds, including iPrMgBr, MeMgBr and BnMgBr. The reaction of the enantiomerically pure N-sulfinylimines 3a and 3b with aliphatic organometallic nucleophiles resulted in

Structure–property relationships and third-order nonlinearities in diketopyrrolopyrrole based D–π–A–π–D molecules

• Jan Podlesný,
• Lenka Dokládalová,
• Oldřich Pytela,
• Adam Urbanec,
• Milan Klikar,
• Numan Almonasy,
• Tomáš Mikysek,
• Jaroslav Jedryka,
• Iwan V. Kityk and
• Filip Bureš

Beilstein J. Org. Chem. 2017, 13, 2374–2384, doi:10.3762/bjoc.13.235

• -photon absorbers (2PA). In this respect, the central DPP bicyclic lactam is often decorated with electron donors such as alkoxy- or dialkylamino groups [11][12], triphenylamine [13][14], heterocyclic carbazole [15], thiophene [16][17], furan [18], and organometallic ferrocene [19]. 2PA-active DPPs were

• substituent shifts the EHOMO to more positive values, slightly deepened ELUMO, and reduces the ΔE within the order of 1 (dimethylanilino) > 2 (4-methoxyphenyl) > 4 (5-methoxythiophen-2-yl) > 3 (thiophen-2-yl). The organometallic ferrocene in 5b caused reduction of the HOMO–LUMO gap up to 1.47 eV and proved to

• and 3b/4b) and are not capable to properly calculate organometallic ferrocene derivatives 5b. However, this is its common feature [45][46]. Conclusion In conclusion, we have designed a series of diketopyrrolopyrrole derivatives having D–π–A–π–D arrangement. Nine new chromophores were conveniently and

Solvent-free copper-catalyzed click chemistry for the synthesis of N-heterocyclic hybrids based on quinoline and 1,2,3-triazole

• Martina Tireli,
• Silvija Maračić,
• Stipe Lukin,
• Marina Juribašić Kulcsár,
• Dijana Žilić,
• Mario Cetina,
• Ivan Halasz,
• Silvana Raić-Malić and
• Krunoslav Užarević

Beilstein J. Org. Chem. 2017, 13, 2352–2363, doi:10.3762/bjoc.13.232

• while monitoring the reaction course by in situ Raman spectroscopy [45]. While this methodology was already successfully applied for establishing mechanistic and kinetic details in the formation of cocrystals [46], coordination and organometallic compounds [47], it proved to be especially valuable for

Conjugated nitrosoalkenes as Michael acceptors in carbon–carbon bond forming reactions: a review and perspective

• Yaroslav D. Boyko,
• Valentin S. Dorokhov,
• Alexey Yu. Sukhorukov and
• Sema L. Ioffe

Beilstein J. Org. Chem. 2017, 13, 2214–2234, doi:10.3762/bjoc.13.220

• intermediate 45, which was subjected to Wittig olefination. Subsequent aza-Sakurai cyclization of intermediate 46 provided tricyclic derivative 47 as a single stereoisomer, which was then transformed into target myrioneurinol by standard operations. Addition of organometallic reagents to conjugated

• nitrosoalkenes The addition of organometallic compounds to conjugated nitrosoalkenes is a promising strategy towards various α-branched oximes. Unfortunately, these reactions are not sufficiently developed to date and only few reports dealing with a successful Michael addition of organometallic compounds to α

• -position and an excess (5 equivalents) of organometallic compound is needed, the reaction is believed to proceed through nitrosoalkene intermediate NSA11. The reaction proved to be efficient yielding the desired β-hydroxyoximes 54 in high yields (80–90%). Interestingly, with cyclohexenone oxime excellent