Life lessons

• Jonathan R. Nitschke

Beilstein J. Org. Chem. 2015, 11, 2350–2354, doi:10.3762/bjoc.11.256

• zirconocene-mediated macrocyclization reactions to make a series of new structures under thermodynamic control, two examples of which are shown in Scheme 1 [1][2]. This Ph.D. work gave me a taste for organic chemistry involving transition metals, and an interest in structures that form under conditions of

Efficient synthetic protocols for the preparation of common N-heterocyclic carbene precursors

• Morgan Hans,
• Jan Lorkowski,
• Albert Demonceau and
• Lionel Delaude

Beilstein J. Org. Chem. 2015, 11, 2318–2325, doi:10.3762/bjoc.11.252

• N-heterocyclic carbenes (NHCs) have become a staple of modern synthetic chemistry [3][4][5][6][7]. Over the past twenty five years, they have evolved from laboratory curiosities to ubiquitous ancillary ligands, not only for all the transition metals whether in high or low oxidation state [8][9][10

Recent advances in copper-catalyzed C–H bond amidation

• Jie-Ping Wan and
• Yanfeng Jing

Beilstein J. Org. Chem. 2015, 11, 2209–2222, doi:10.3762/bjoc.11.240

• accordingly received significant progress by making use of the coupling between amino group and inert C–H bonds [34][35]. Considering the notable advances that have happened in the research of C–H amidation, it is desirable to provide a review work on this issue. Although different transition metals are known

Easy access to heterobimetallic complexes for medical imaging applications via microwave-enhanced cycloaddition

• Nicolas Desbois,
• Sandrine Pacquelet,
• Adrien Dubois,
• Clément Michelin and
• Claude P. Gros

Beilstein J. Org. Chem. 2015, 11, 2202–2208, doi:10.3762/bjoc.11.239

• chosen two porphyrinoid derivatives that are easy to prepare in only a few steps: an azidocorrole 1 [9] and an azidoporphyrin 2 [10] (Figure 1). Porphyrins and corroles display interesting properties in terms of metal complexation of, e.g., transition metals. We have selected two commercial available

C–H bond halogenation catalyzed or mediated by copper: an overview

• Wenyan Hao and
• Yunyun Liu

Beilstein J. Org. Chem. 2015, 11, 2132–2144, doi:10.3762/bjoc.11.230

• , significant advances have also occurred in the C–H halogenation catalyzed by different transition metals as Pd [19][20][21][22][23], Rh [24][25], Ru [26], Au [27], Co [28], etc. As a class of readily available and ubiquitously employed transition metal catalysts, copper catalysts have exhibited tremendous

Olefin metathesis in air

• Lorenzo Piola,
• Fady Nahra and
• Steven P. Nolan

Beilstein J. Org. Chem. 2015, 11, 2038–2056, doi:10.3762/bjoc.11.221

• , late transition metals, which do not exhibit high oxophilicity, appeared as the most promising candidates for reactions performed in air. Indeed in 1988, Grubbs and Novak reported that not only ruthenium was an interesting candidate for olefin metathesis, but also that reactions were successfully

Copper-catalyzed aerobic radical C–C bond cleavage of N–H ketimines

• Ya Lin Tnay,
• Gim Yean Ang and
• Shunsuke Chiba

Beilstein J. Org. Chem. 2015, 11, 1933–1943, doi:10.3762/bjoc.11.209

• appropriate lower valent transition metals [28][29][30][31][32], electron-rich organic electron donors [33][34][35][36][37][38], or sensitized photolysis [39][40][41][42] (Scheme 1c). Although the oxidative generation of iminyl radicals has also been reported, only iminooxyacetic acids have been used as the

Profluorescent substrates for the screening of olefin metathesis catalysts

• Raphael Reuter and
• Thomas R. Ward

Beilstein J. Org. Chem. 2015, 11, 1886–1892, doi:10.3762/bjoc.11.203

• recent applications, metathesis has also been used in chemical biology, either in the form of an artificial metalloenzyme [8][9][10] or for the post-translational modification of proteins [11]. To address these various challenges, a vast number of carbene complexes based on different transition metals

The facile construction of the phthalazin-1(2H)-one scaffold via copper-mediated C–H(sp²)/C–H(sp) coupling under mild conditions

• Wei Zhu,
• Bao Wang,
• Shengbin Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2015, 11, 1624–1631, doi:10.3762/bjoc.11.177

• the viewpoint of practicality and feasibility, increasing attention was paid to develop cheap and easily available transition metals, such as copper, to realize direct C–H functionalization [17]. Miura and Yu successfully demonstrated a novel protocol for the direct C–H/C–H coupling with combinations

Preparative semiconductor photoredox catalysis: An emerging theme in organic synthesis

• David W. Manley and
• John C. Walton

Beilstein J. Org. Chem. 2015, 11, 1570–1582, doi:10.3762/bjoc.11.173

• natural products and pharmaceuticals. Transition metals are very successful in catalyzing homo-couplings, particularly for sp2 hybridized C-centers. Radical-based dimerizations are also known to be effective and offer the opportunity to extend the scope to sp3 centers. TiO2 photoredox reactions with

Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF₅-substituted phenylboronic esters and iodobenzenes

• George Iakobson,
• Junyi Du,
• Alexandra M. Z. Slawin and
• Petr Beier

Beilstein J. Org. Chem. 2015, 11, 1494–1502, doi:10.3762/bjoc.11.162

• -phenylboronates where our methodology represents a considerable improvement in reaction efficiency compared to previously published syntheses. Furthermore, no transition metals are needed and mild reaction conditions are used. The borylation is applicable to a variety of aryldiazonium tetrafluoroborates with

New palladium–oxazoline complexes: Synthesis and evaluation of the optical properties and the catalytic power during the oxidation of textile dyes

• Rym Hassani,
• Mahjoub Jabli,
• Yakdhane Kacem,
• Jérôme Marrot,
• Damien Prim and
• Béchir Ben Hassine

Beilstein J. Org. Chem. 2015, 11, 1175–1186, doi:10.3762/bjoc.11.132

• one oxazoline ring [6]. Oxazoline units are expected to readily coordinate to a metal center and have been shown to bind a wide range of transition metals [7]. The wide variety of ligands with one or more oxazoline rings incorporating different heteroatoms, additional chiral groups, and specific

Synthesis and characterization of the cyanobenzene-ethylenedithio-TTF donor

• Sandrina Oliveira,
• Dulce Belo,
• Isabel C. Santos,
• Sandra Rabaça and
• Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 951–956, doi:10.3762/bjoc.11.106

• allows a possible 2D or 3D character to the electronic interactions. More recently there has been an increasing interest in TTF derivatives containing N atoms in their periphery which, while retaining the electroactive behaviour of TTF, could also be able to coordinate to transition metals [3][4][5][6][7

TTFs nonsymmetrically fused with alkylthiophenic moieties

• Rafaela A. L. Silva,
• Bruno J. C. Vieira,
• Marta M. Andrade,
• Isabel C. Santos,
• Sandra Rabaça,
• Dulce Belo and
• Manuel Almeida

Beilstein J. Org. Chem. 2015, 11, 628–637, doi:10.3762/bjoc.11.71

• analogous transition metals complexes, enabling their processing from solutions. Results and Discussion Synthesis The TTF donors fused non-symetrically with substituted thiophene moieties 1 and 2 were obtained by the cross coupling, in the presence of trimethyl phosphite, between compounds I and II and

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

• Katherine M. Byrd

Beilstein J. Org. Chem. 2015, 11, 530–562, doi:10.3762/bjoc.11.60

• of boron to α,β-unsaturated carbonyl compounds. Enantioenriched organoboron reagents are useful because they can be used in cross-coupling reactions [98][100] or they can be converted into the corresponding alcohol [101] while retaining the stereochemical information. Transition metals such as Cu

• [102][103][104][105][106][107][108][109][110][111][112], Rh [113][114][115], Ni [116][117], Pd [116][118] and Pt [119][120] have all been successfully used to catalyze the 1,4-additon of boron to α,β-unsaturated carbonyl compounds. Of the transition metals mentioned, copper is the most cost-effective

• -unsaturated amides and lactams, which remains an area that is underdeveloped. 2.3 Other transition-metal-catalyzed ECA reactions Though the majority of the reports on ECA of α,β-unsaturated amides and lactams utilize copper and rhodium as catalysts, other transition metals have also been used in these

Electrochemical selenium- and iodonium-initiated cyclisation of hydroxy-functionalised 1,4-dienes

• Philipp Röse,
• Steffen Emge,
• Jun-ichi Yoshida and
• Gerhard Hilt

Beilstein J. Org. Chem. 2015, 11, 174–183, doi:10.3762/bjoc.11.18

• ; Introduction The reaction of terminal alkenes with 1,3-dienes under cobalt catalysis results in 1,4-dienes in a 1,4-hydrovinylation reaction. Besides cobalt, also other transition metals were described to undergo such transformations [1][2][3][4]. However, only for the cobalt-catalysed reactions a regiodiverse

Lewis acid-catalyzed redox-neutral amination of 2-(3-pyrroline-1-yl)benzaldehydes via intramolecular [1,5]-hydride shift/isomerization reaction

• Chun-Huan Jiang,
• Xiantao Lei,
• Le Zhen,
• Hong-Jin Du,
• Xiaoan Wen,
• Qing-Long Xu and
• Hongbin Sun

Beilstein J. Org. Chem. 2014, 10, 2892–2896, doi:10.3762/bjoc.10.306

• : catalysis; C–H activation; hydride-shift; Lewis acid; redox reaction; Introduction The direct and selective functionalization of the inactive C(sp3)–H bond constitute an economically attractive strategy for organic syntheses [1][2][3][4][5][6][7][8][9][10]. Until now, a number of transition metals can be

Preparation of phosphines through C–P bond formation

• Iris Wauters,
• Wouter Debrouwer and
• Christian V. Stevens

Beilstein J. Org. Chem. 2014, 10, 1064–1096, doi:10.3762/bjoc.10.106

• hydrophosphinations. Metal complex-catalyzed hydrophosphinations Hydrophosphination catalysts are mainly based on transition metals. However, it has been shown that lanthanides and alkaline earth metals can offer a valid alternative. Palladium and nickel complexes were used to catalyze the addition of the P–H bond to

Domino reactions of 2H-azirines with acylketenes from furan-2,3-diones: Competition between the formation of ortho-fused and bridged heterocyclic systems

• Alexander F. Khlebnikov,
• Mikhail S. Novikov,
• Viktoriia V. Pakalnis,
• Roman O. Iakovenko and
• Dmitry S. Yufit

Beilstein J. Org. Chem. 2014, 10, 784–793, doi:10.3762/bjoc.10.74

• -system (4.56, 4.68 ppm). Attempts to initiate the reaction by UV-irradiation (at 20 or 50 °C) or catalysis by compounds of transition metals (Cu(acac)2, Fe(acac)3, Pd(bzac)2, Rh2(AcO)4, Cu(OTf)2, Pd/C) at 20 or 40 °C failed. Benzene was found to be a solvent of choice, and a 1:1 molar ratio of reagents

Isocyanide-based multicomponent reactions towards cyclic constrained peptidomimetics

• Gijs Koopmanschap,
• Eelco Ruijter and
• Romano V.A. Orru

Beilstein J. Org. Chem. 2014, 10, 544–598, doi:10.3762/bjoc.10.50

• these three steps simultaneously in one-pot, however, as isocyanides are also good ligands to transition metals, the Ugi products were only obtained in low yield (19%) without observing any triazole product. Even more interestingly was the copper-free procedure published by the group of Cai, especially

Silver and gold-catalyzed multicomponent reactions

• Giorgio Abbiati and
• Elisabetta Rossi

Beilstein J. Org. Chem. 2014, 10, 481–513, doi:10.3762/bjoc.10.46

• involving higher oxidation states from Au(I) precatalysts have been achieved by the addition of a stoichiometric oxidant enabling two-electron redox cycles typically exhibited by other late transition metals. With respect to Ag(I)-mediated MCRs, less information can be found in the literature about the

Garner’s aldehyde as a versatile intermediate in the synthesis of enantiopure natural products

• Mikko Passiniemi and
• Ari M.P. Koskinen

Beilstein J. Org. Chem. 2013, 9, 2641–2659, doi:10.3762/bjoc.9.300

• nucleophiles seem to give a roughly 8:1 anti/syn-selectivity. The larger organovinyl reagents give slightly lower anti-selectivities of about 3:1 to 5:1. Highest selectivities are reached with transition metals, such as Rh and Ni (Table 1, entries 12, 18 and 19). The anti-selectivity can be enhanced either by

New developments in gold-catalyzed manipulation of inactivated alkenes

• Michel Chiarucci and
• Marco Bandini

Beilstein J. Org. Chem. 2013, 9, 2586–2614, doi:10.3762/bjoc.9.294

• strategies Differently from many transition metals, usually gold is not subjected to redox processes during the catalytic cycles. However, in recent years it has been demonstrated that both [Au(I)/Au(III)] (i.e. monometallic catalytic systems) and [Au(I)Au(I)/Au(II)Au(II)] (i.e. bimetallic catalytic systems

Recent advances in transition metal-catalyzed Csp²-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation

• Grégory Landelle,
• Armen Panossian,
• Sergiy Pazenok,
• Jean-Pierre Vors and
• Frédéric R. Leroux

Beilstein J. Org. Chem. 2013, 9, 2476–2536, doi:10.3762/bjoc.9.287

• moieties have been reported in the literature [27][33][34][35][36][37][38][39][40][41], the incorporation of partially fluorinated methyl groups is still underdeveloped [42][43]. In most cases transition metals have to be employed in stoichiometric amounts. 1.1 Palladium catalysis The first

Gold(I)-catalyzed enantioselective cycloaddition reactions

• Fernando López and
• José L. Mascareñas

Beilstein J. Org. Chem. 2013, 9, 2250–2264, doi:10.3762/bjoc.9.264

• core of frondosins (for example, 5a), in 68% yield and 90% ee (Scheme 4). Since this bicyclic enone was previously elaborated into frondosin A and B, the approach represented a streamlined formal enantioselective synthesis of both molecules. Analogous to other transition metals from groups eight to