Thiol-free chemoenzymatic synthesis of β-ketosulfides

• Adrián A. Heredia,
• Martín G. López-Vidal,
• Marcela Kurina-Sanz,
• Fabricio R. Bisogno and
• Alicia B. Peñéñory

Beilstein J. Org. Chem. 2019, 15, 378–387, doi:10.3762/bjoc.15.34

• ][40]. Such a combination has been scarcely exploited as compared to strategies comprising transition metal catalysis and biocatalysis [41] or, in a lesser extent, organocatalysis and enzymes [42]. In this context, a versatile and robust synthesis of β-ketosulfides avoiding the use of thiols under

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

• reaction may cause skin damage to experimenters. Alternatively, alkynes (Scheme 1b) played an important role in the synthesis of phenanthrene scaffolds under transition metal catalysis [9]. However, this protocol required complicated procedures, harsh reaction conditions and was incompatible with many

Synthesis of 1,2-divinylcyclopropanes by metal-catalyzed cyclopropanation of 1,3-dienes with cyclopropenes as vinyl carbene precursors

• Jesús González,
• Alba de la Fuente,
• María J. González,
• Laura Díez de Tejada,
• Luis A. López and
• Rubén Vicente

Beilstein J. Org. Chem. 2019, 15, 285–290, doi:10.3762/bjoc.15.25

• ; transition metal catalysis; Introduction Far from being considered exotic molecules, cyclopropane derivatives constitute an interesting class of compounds. Indeed, far over 4000 natural products bearing a cyclopropane ring have been discovered [1][2][3], and cyclopropane-containing molecules are recurrent

The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT study

• Magdalena Jawiczuk,
• Angelika Janaszkiewicz and
• Bartosz Trzaskowski

Beilstein J. Org. Chem. 2018, 14, 2872–2880, doi:10.3762/bjoc.14.266

• carbene (NHC) by Arduengo [1] was a milestone in organic chemistry which allowed for thorough and systematic studies on all aspects of NHC chemistry in the past 25 years [2][3][4][5][6][7]. It was soon realized that NHCs are a very useful class of ligands for transition metal catalysis as both their

Molecular iodine-catalyzed one-pot multicomponent synthesis of 5-amino-4-(arylselanyl)-1H-pyrazoles

• Camila S. Pires,
• Daniela H. de Oliveira,
• Maria R. B. Pontel,
• Jean C. Kazmierczak,
• Roberta Cargnelutti,
• Diego Alves,
• Raquel G. Jacob and
• Ricardo F. Schumacher

Beilstein J. Org. Chem. 2018, 14, 2789–2798, doi:10.3762/bjoc.14.256

• combine at least two bioactive moieties in one molecule avoiding residual metal in transition-metal catalysis in environmental benign conditions is desired. Recently, Sun and co-workers described their interesting results on the I2-catalyzed efficient synthesis of 5-amino-4-sulfanylpyrazoles using diverse

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

• C–H bonds has been identified as one of the key challenges in modern day chemical research [1][2][3], providing the potential to access complex chemical structures more efficiently. In this context, transition metal catalysis is seen as a potential solution, building on the traditional and well

Recent applications of chiral calixarenes in asymmetric catalysis

• Mustafa Durmaz,
• Erkan Halay and
• Selahattin Bozkurt

Beilstein J. Org. Chem. 2018, 14, 1389–1412, doi:10.3762/bjoc.14.117

• which the chirality is induced by attaching chiral groups to the calixarene backbone is more common and the obtained results are more promising. In addition, the calix[4]arene backbone is much more preferred beyond other ring sizes both in transition metal catalysis and organocatalysis. It can be argued

Photocatalytic formation of carbon–sulfur bonds

• Alexander Wimmer and
• Burkhard König

Beilstein J. Org. Chem. 2018, 14, 54–83, doi:10.3762/bjoc.14.4

• formation of C–S bonds was published by Oderinde, Johannes and co-workers. They combined photoredox catalysis with transition metal catalysis [52][53][54][55] for the formation of C–S bonds (Scheme 21) [56]. The reaction proceeds via two different catalytic cycles: The photo-excited state of the [Ir(dF(CF3

Transition-metal-free one-pot synthesis of alkynyl selenides from terminal alkynes under aerobic and sustainable conditions

• Adrián A. Heredia and
• Alicia B. Peñéñory

Beilstein J. Org. Chem. 2017, 13, 910–918, doi:10.3762/bjoc.13.92

• , which limit their application. Furthermore, in most cases these procedures involve the use of reducing agents, such as elemental Mg or Zn, transition-metal catalysis, inert atmosphere, controlled temperatures, and long reaction times. Recently, we have reported the synthesis of vinyl selenides 1 by a

The reductive decyanation reaction: an overview and recent developments

• Jean-Marc R. Mattalia

Beilstein J. Org. Chem. 2017, 13, 267–284, doi:10.3762/bjoc.13.30

• advantages of the nitrile functional group before its removal. Mechanistic details and applications to organic synthesis are provided. Keywords: α-aminonitrile; decyanation; electron donor; hydride; malononitrile; transition metal catalysis; Introduction Many strategies in organic synthesis involve the

Construction of bis-, tris- and tetrahydrazones by addition of azoalkenes to amines and ammonia

• Artem N. Semakin,
• Aleksandr O. Kokuev,
• Yulia V. Nelyubina,
• Alexey Yu. Sukhorukov,
• Petr A. Zhmurov,
• Sema L. Ioffe and
• Vladimir A. Tartakovsky

Beilstein J. Org. Chem. 2016, 12, 2471–2477, doi:10.3762/bjoc.12.241

• (hydrazonomethyl)amines I and their applications as ligands in transition metal catalysis are currently underway. Selected examples of polyhydrazones. Structures of polyhydrazones 3-9. Methods: A: 1 equiv of amine, 2 equiv of 1a, 2 equiv of K2CO3; B; 1 equiv of amine, 1 equiv of 1a, 1 equiv of K2CO3; C; 1 equiv of

Ionic liquids as transesterification catalysts: applications for the synthesis of linear and cyclic organic carbonates

• Maurizio Selva,
• Alvise Perosa,
• Sandro Guidi and
• Lisa Cattelan

Beilstein J. Org. Chem. 2016, 12, 1911–1924, doi:10.3762/bjoc.12.181

• in terms of environmental impact, safety and economics. Thus, by the end of the 1990’s, two main phosgene-free large-capacity processes were operative, both based on the incorporation of carbon monoxide (CO) and methanol by transition metal catalysis: one developed by EniChem [57][58], and the other

• necessarily require transition metal catalysis as did the EniChem and Ube processes. Instead, the reaction can be effectively catalyzed by a combination of supported basic ammonium resins and homogeneous alkaline bases [60], thereby demonstrating the potential of transition metal-free catalytic systems for

Catalytic asymmetric synthesis of biologically important 3-hydroxyoxindoles: an update

• Bin Yu,
• Hui Xing,
• De-Quan Yu and
• Hong-Min Liu

Beilstein J. Org. Chem. 2016, 12, 1000–1039, doi:10.3762/bjoc.12.98

• , enantioenriched 3-hydroxyoxindole scaffolds also exist in natural products and have proven to possess promising biological activities. A large number of catalytic asymmetric strategies toward the construction of 3-hydroxyoxindoles based on transition metal catalysis and organocatalysis have been reported in the

• -substituted 3-hydroxyoxindoles and 3-hydroxyoxindole-based further transformations. Keywords: 3-hydroxyoxindoles; oxindoles; organocatalysis; spirooxindoles; transition metal catalysis; Introduction Chiral oxindoles are an important class of compounds, which widely exist in nature and have exhibited diverse

The synthesis of functionalized bridged polycycles via C–H bond insertion

• Jiun-Le Shih,
• Po-An Chen and
• Jeremy A. May

Beilstein J. Org. Chem. 2016, 12, 985–999, doi:10.3762/bjoc.12.97

• have organized this review by the catalyst used, with free carbenes first, followed by Cu, Rh, Au, Pt, and then W-catalyzed reactions. Review Metal-free reactions While transition metal catalysis has seen widespread adoption for carbene and nitrene reactions, it is not necessary for a controlled

• [31]. Metal-catalyzed reactions Copper The earliest example to our knowledge of transition metal catalysis for the formation of bridged rings via C–H bond insertion was Wolff’s use of copper (Scheme 6) [32][33]. Silver was also examined as a possible catalyst, but then a Wolff rearrangement was the

Recent advances in C(sp³)–H bond functionalization via metal–carbene insertions

• Bo Wang,
• Di Qiu,
• Yan Zhang and
• Jianbo Wang

Beilstein J. Org. Chem. 2016, 12, 796–804, doi:10.3762/bjoc.12.78

• –carbene; site-selectivity; Introduction Direct functionalization of inactivated C–H bonds, especially C(sp3)–H bonds, have attracted significant attentions in recent years. The C(sp3)–H bond activation strategies based on radical reactions and transition metal catalysis have been explored, alongside the

Base metal-catalyzed benzylic oxidation of (aryl)(heteroaryl)methanes with molecular oxygen

• Hans Sterckx,
• Johan De Houwer,
• Carl Mensch,
• Wouter Herrebout,
• Kourosch Abbaspour Tehrani and
• Bert U. W. Maes

Beilstein J. Org. Chem. 2016, 12, 144–153, doi:10.3762/bjoc.12.16

• features two oxidation sensitive veratrole units. Interestingly, a highly chemoselective oxidation was observed and compound 15 was isolated in 60% yield. Trace metal analysis When using transition metal catalysis in the synthesis of compounds designated for application (pharmaceuticals, agrochemicals

Synthesis of bi- and bis-1,2,3-triazoles by copper-catalyzed Huisgen cycloaddition: A family of valuable products by click chemistry

• Zhan-Jiang Zheng,
• Ding Wang,
• Zheng Xu and
• Li-Wen Xu

Beilstein J. Org. Chem. 2015, 11, 2557–2576, doi:10.3762/bjoc.11.276

• , functional ligands often play a key role in transition metal catalysis. Accordingly, the bistriazole derivatives could provide promising alternatives to bipyridine ligands because of their powerful nitrogen-centered coordination. In this context, Hao and co-workers have reported bistriazole-based N4

Come-back of phenanthridine and phenanthridinium derivatives in the 21st century

• Lidija-Marija Tumir,
• Marijana Radić Stojković and
• Ivo Piantanida

Beilstein J. Org. Chem. 2014, 10, 2930–2954, doi:10.3762/bjoc.10.312

• ][21][22][23][24] and the synthesis based on transition metal-catalysis [15][27][28][29][30][31][32][33][34][35][36][37]. The main advantage of the radical-based phenanthridine synthesis is easy available and generally cheap starting material (benzotriazole, aminobiphenyl, arylaldehyde, N-(ortho

• -alkylphenanthridine derivatives and 6-phosphorylated analogues, equipped with one or two additional substituents, usually positioned on the phenanthridine positions C1–4 or position C8. Similarly to the radical-based synthesis, a synthetic approach based on transition metal-catalysis also allows the phenanthridine

P(O)R₂-directed Pd-catalyzed C–H functionalization of biaryl derivatives to synthesize chiral phosphorous ligands

• Rong-Bin Hu,
• Hong-Li Wang,
• Hong-Yu Zhang,
• Heng Zhang,
• Yan-Na Ma and
• Shang-dong Yang

Beilstein J. Org. Chem. 2014, 10, 2071–2076, doi:10.3762/bjoc.10.215

• prefunctionalization or lithiation of substrate. However, these methods are not compatible for some activated functional groups in precursor compounds. Over the past several years, we have achieved reactions of C–P bond formation with new and efficient protocols via transition metal-catalysis [11][12][13][14][15][16

Rational design of cyclopropane-based chiral PHOX ligands for intermolecular asymmetric Heck reaction

• Marina Rubina,
• William M. Sherrill,
• Alexey Yu. Barkov and
• Michael Rubin

Beilstein J. Org. Chem. 2014, 10, 1536–1548, doi:10.3762/bjoc.10.158

• the isomerization were identified. It was shown that the nature of this isomerization is different from that demonstrated previously using chiral diphosphine ligands. Keywords: asymmetric catalysis; chiral phosphine ligands; cyclopropane; Heck reaction; organophosphorus; transition metal catalysis

The Ugi four-component reaction as a concise modular synthetic tool for photo-induced electron transfer donor-anthraquinone dyads

• Sarah Bay,
• Gamall Makhloufi,
• Christoph Janiak and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2014, 10, 1006–1016, doi:10.3762/bjoc.10.100

• diversity-oriented syntheses of chromophores [62][63][64][65][66][67][68][69] we have established accesses to chromophores in a one-pot fashion based upon transition metal catalysis as an entry to consecutive multicomponent [70][71] and domino reactions [72]. The highly convergent synthetic approach by

New hydrogen-bonding organocatalysts: Chiral cyclophosphazanes and phosphorus amides as catalysts for asymmetric Michael additions

• Helge Klare,
• Jörg M. Neudörfl and
• Bernd Goldfuss

Beilstein J. Org. Chem. 2014, 10, 224–236, doi:10.3762/bjoc.10.18

• ; Chakravarty et al. [24] tested an ansa-bridged BINOL-based PV-cyclodiphosphazane in the asymmetric reduction of acetophenone with BH3 (5–8% ee), while Gade et al. [25] recently introduced BINOL-based PIII-cyclodiphosphazane ligands to transition-metal catalysis (up to 84% ee). We anticipated that by

Recent applications of the divinylcyclopropane–cycloheptadiene rearrangement in organic synthesis

• Sebastian Krüger and
• Tanja Gaich

Beilstein J. Org. Chem. 2014, 10, 163–193, doi:10.3762/bjoc.10.14

• give intermediate vinyl-allenecyclopropane 249, followed by a DVCPR to furnish cycloheptadiene 250. 1,2-Shift and vinyl-carbenoid formation sequences Two major pathways to generate divinylcyclopropanes using transition metal catalysis have been developed. Uemura and coworkers [204] were the first to

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

An investigation of the observed, but counter-intuitive, stereoselectivity noted during chiral amine synthesis via N-chiral-ketimines

• Thomas C. Nugent,
• Richard Vaughan Williams,
• Andrei Dragan,
• Alejandro Alvarado Méndez and
• Andrei V. Iosub

Beilstein J. Org. Chem. 2013, 9, 2103–2112, doi:10.3762/bjoc.9.247

• transition metal catalysis [5][6][7][8] and as resolving agents [9]. Despite their high demand, the ability to produce structurally diverse chiral amines has not kept pace. Spurred by this shortcoming, innovative and improved chemical methods have been developed over the last fifteen years. Among them