Phosphonic acid: preparation and applications

• Charlotte M. Sevrain,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2017, 13, 2186–2213, doi:10.3762/bjoc.13.219

• phosphorus-containing functional groups [2], on specific applications (hybrid materials [3], surface modification [4], oil industry [5]) or dedicated to a family of compounds (e.g., aminophosphonic acids [6], organometallic phosphonic acids [7]). However, no recent review was focused on the different methods

• develop bone targeting which was assessed for therapy [96] and imaging [97][98]. Finally, the phosphonic acid group was also employed to immobilize organic or organometallic molecules on the surface of metal oxide [99][100] (Al2O3 [101], TiO2 [102][103], SnO2 [104], Fe3O4 [105], ZnO [106]), CdSe quantum

• dendrimers 67 [192]. The use of BrSiMe3 was also applied to diverse organometallic compounds as exemplified in Figure 20. This procedure was applicable to compounds featuring CpFe(CO)2 68 [193] or ferrocenyl 69 [194][195] moieties but also to palladium or platinium pincer complexes 70 [196] or arene–chrome

The effect of milling frequency on a mechanochemical organic reaction monitored by in situ Raman spectroscopy

• Patrick A. Julien,
• Ivani Malvestiti and
• Tomislav Friščić

Beilstein J. Org. Chem. 2017, 13, 2160–2168, doi:10.3762/bjoc.13.216

• , have emerged as a highly versatile and general route to conduct chemical reactions in the absence of bulk solvents [2]. Indeed, the demonstrated versatility in organic [5][6][7][8], organometallic [9][10], pharmaceutical [11][12], supramolecular [13], metal-organic [14][15], and materials synthesis [16

Main group mechanochemistry

• Agota A. Gečiauskaitė and
• Felipe García

Beilstein J. Org. Chem. 2017, 13, 2068–2077, doi:10.3762/bjoc.13.204

• sustainable alternatives to conventional solvent-based synthetic routes. Mechanochemistry has already been successfully applied to the synthesis of active pharmaceutical ingredients (APIs), organic compounds, metal oxides, coordination compounds and organometallic complexes. In the main group arena, examples

• , and during the last 25 years, mechanochemical methods have been applied to various fields, including catalysis [47], organic synthesis [5][7][48][49], metal-organic frameworks (MOFs) [50][51], coordination [52], organometallic [11], supramolecular [53], environmental [54][55], APIs [56], medicinal [57

• . In the field of organometallic chemistry, we highlight the large-scale synthesis of SrCp′2(OEt2) (Cp′ = C5Me4(n-Pr)) (1) [82], an ideal precursor for the chemical vapour deposition (CVD) of strontium-based semiconductors – a key material in memory devices [83]. Previously, this compound could only be

Mechanochemical synthesis of small organic molecules

• Tapas Kumar Achar,
• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2017, 13, 1907–1931, doi:10.3762/bjoc.13.186

• (C–X), etc. is documented. Mechanochemical syntheses of heterocyclic rings, multicomponent reactions and organometallic molecules including their catalytic applications are also highlighted. Keywords: ball-milling; green chemistry; mechanochemistry; solid-phase synthesis; solvent-free synthesis

• bond formation reactions, multicomponent reactions, heterocyclic ring synthesis, synthesis of organometallic complexes and their catalytic applications, and so on. Review Mechanochemical organic synthesis Famous philosopher Aristotle’s statement “No Coopora nisi Fluida” means ‘no reaction is possible

• transition metals, could be performed in shorter reaction time and uses stable dichalcogenides rather than toxic thiols and selenols. Organometallic synthesis and catalytic application Mechano-synthesis of organometallic compounds The last decade has witnessed a rapid growth of mechanochemistry in organic

Solvent-free sonochemistry: Sonochemical organic synthesis in the absence of a liquid medium

• Deborah E. Crawford

Beilstein J. Org. Chem. 2017, 13, 1850–1856, doi:10.3762/bjoc.13.179

• layered materials such as graphite (to form graphene) [10], but it has also been employed in the formation of organometallic [11] and organic compounds [12]. Great success has been found in the treatment of waste water by ultrasonic irradiation, to remove heavy metals or degrade aromatic constituents [13

Effect of uridine protecting groups on the diastereoselectivity of uridine-derived aldehyde 5’-alkynylation

• Raja Ben Othman,
• Mickaël J. Fer,
• Laurent Le Corre,
• Sandrine Calvet-Vitale and
• Christine Gravier-Pelletier

Beilstein J. Org. Chem. 2017, 13, 1533–1541, doi:10.3762/bjoc.13.153

• organometallic reagents onto nucleoside aldehyde (Table 1), we decided to investigate the influence of the protecting groups of the uridine aldehyde on the stereochemical outcome of the nucleophilic addition of a Grignard reagent and we wish to report herein the results of our study. Results and Discussion We

• organometallic reagent on nucleoside aldehydes. Influence of the protecting groups and conditions on the diastereoselectivity of the alkynyl Grignard addition on uridine derived aldehydes. Supporting Information Supporting Information File 107: Description of the materials and methods, and the preparation and

Synthesis of alkynyl-substituted camphor derivatives and their use in the preparation of paclitaxel-related compounds

• M. Fernanda N. N. Carvalho,
• Rudolf Herrmann and
• Gabriele Wagner

Beilstein J. Org. Chem. 2017, 13, 1230–1238, doi:10.3762/bjoc.13.122

• the addition of organometallic reagents to the camphor carbonyl group allows for selective introduction of additional substituents and functional groups (e.g., as in [7]). Camphor was the source of chirality in Holton’s taxol synthesis [8] and other approaches to the taxane group of compounds [9][10

Total syntheses of the archazolids: an emerging class of novel anticancer drugs

• Stephan Scheeff and
• Dirk Menche

Beilstein J. Org. Chem. 2017, 13, 1085–1098, doi:10.3762/bjoc.13.108

• . Notably, they had to switch the halide/organometallic functionality of each building block after an unsuccessful coupling between the stannane synthesized by reduction and methylation of ketone 67 and the iodine derived from fragment 62. They assume that the steric hindrance of the methyl group in C10

• already coupled a similar fragment 70 with the southern fragment 57 by an organometallic addition, however, with a lack of stereoselectivity in C23 position [45]. As shown in Scheme 14, they started with the deprotection of the primary TBS ether 70 and DMP oxidation to the aldehyde 71. The bromide 57

• . Final steps of Trauner’s total synthesis of archazolid B. Overview of the different retrosynthetic approaches for the synthesis of dihydroarchazolid B (3) reported by the O'Neil group. Fragment synthesis of 69 towards the total synthesis of 3. Organometallic addition of the side chain to access free

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

• reactions to alkynyl selenides in the absence of transition metals [16] and the addition of p-toluenesulfonic acid [17] are applied to obtain vinyl organometallic compounds and key selenoester intermediates. Finally, electrophilic cyclizations [18][19] of systems bearing a selenide alkynyl group allow the

Substitution of fluorine in M[C₆F₅BF₃] with organolithium compounds: distinctions between O- and N-nucleophiles

• Anton Yu. Shabalin,
• Nicolay Yu. Adonin and
• Vadim V. Bardin

Beilstein J. Org. Chem. 2017, 13, 703–713, doi:10.3762/bjoc.13.69

• compounds is based on the transformation of polyfluoroarenes under the action of appropriate reagents into the corresponding organometallic derivatives followed by treating them with suitable boron-containing electrophiles (Scheme 1) [28][29]. In order to further expand this powerful tool for the

Synthesis of new pyrrolidine-based organocatalysts and study of their use in the asymmetric Michael addition of aldehydes to nitroolefins

• Alejandro Castán,
• Ramón Badorrey,
• José A. Gálvez and
• María D. Díaz-de-Villegas

Beilstein J. Org. Chem. 2017, 13, 612–619, doi:10.3762/bjoc.13.59

• tuneable catalytic motifs to be used in organocatalysis starting from the chiral pool. Highly modular chiral aminodiol derivatives were obtained by the addition of organometallic reagents to chiral imines derived from (R)-glyceraldehyde – which is easily accessible from D-mannitol – and these were

Contribution of microreactor technology and flow chemistry to the development of green and sustainable synthesis

• Flavio Fanelli,
• Giovanna Parisi,
• Leonardo Degennaro and
• Renzo Luisi

Beilstein J. Org. Chem. 2017, 13, 520–542, doi:10.3762/bjoc.13.51

• -Haloalkyllithiums are a useful class of organometallic reagents widely employed in synthetic chemistry. In fact, they allow the direct homologation of carbonyl compounds and imines leading to β-halo-alcohols and amines that are useful building blocks [29][30][31]. This work represents a remarkable example of flash

• example on the use of microreactor technology for the development of sustainable chemical processes, is represented by the direct introduction of the tert-butoxycarbonyl group into organometallic reagents [34]. The reaction between organolithium reagents and di-tert-butyl dicarbonate run under flow

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

• applied to 72d or a substrate similar to 72e. More recently, the reaction of dibenzylmalononitrile 72b with the hydroxyaryl-substituted benzimidazoline derivative 81 as photo-reductant in a basic medium has been described and led to 73b in fair yield (Scheme 27) [128]. Acid, base or organometallic-induced

• organometallic reagents or other nucleophiles [139]. Nambo et al described the preparation of triarylacetonitriles using sequential Pd-catalyzed arylations. Triarylacetonitriles obtained can be transformed into various species including triarylmethanes by treatment with MeMgCl (Scheme 30) [140]. In this case a

Efficient access to β-vinylporphyrin derivatives via palladium cross coupling of β-bromoporphyrins with N-tosylhydrazones

• Vinicius R. Campos,
• Ana T. P. C. Gomes,
• Anna C. Cunha,
• Maria da Graça P. M. S. Neves,
• Vitor F. Ferreira and
• José A. S. Cavaleiro

Beilstein J. Org. Chem. 2017, 13, 195–202, doi:10.3762/bjoc.13.22

• features – stoichiometric organometallic reagents are not required for the coupling reaction and di- and trisubstituted olefins can be prepared with high stereoselectivity. In fact, N-tosylhydrazones used in this methodology can be easily prepared from carbonyl compounds (Scheme 1), as it has been well

• demonstrated by Barluenga and co-workers [11][26][27]. This methodology allowed the development of novel protocols enabling transformations that are difficult to achieve with other reactions and include other important features as: stoichiometric organometallic reagents are not required for the coupling

Green chemistry

• Luigi Vaccaro

Beilstein J. Org. Chem. 2016, 12, 2763–2765, doi:10.3762/bjoc.12.273

• , including “Strategies in asymmetric catalysis” by Tehshik P. Yoon [6], “Organometallic chemistry” by Bernd F. Straub and Lutz H. Gade [7], “C–H functionalization/activation in organic synthesis” by Richmond Sarpong [8], “Bifunctional catalysis” by Darren J. Dixon [9], “Sustainable catalysis” by Nicholas J

Synthesis of polyhydroxylated decalins via two consecutive one-pot reactions: 1,4-addition/aldol reaction followed by RCM/syn-dihydroxylation

• Michał Malik and
• Sławomir Jarosz

Beilstein J. Org. Chem. 2016, 12, 2602–2608, doi:10.3762/bjoc.12.255

• of this transformation, three new stereogenic centers are generated. A copper-catalyzed 1,4-addition of organometallic reagents to cyclic α,β-unsaturated ketones, followed by an aldol reaction has been already used in the synthesis of complex natural products [26][27][28][29][30][31][32][33

Protonated paramagnetic redox forms of di-o-quinone bridged with p-phenylene-extended TTF: A EPR spectroscopy study

• Nikolay O. Chalkov,
• Vladimir K. Cherkasov,
• Gleb A. Abakumov,
• Andrey G. Starikov and
• Viacheslav A. Kuropatov

Beilstein J. Org. Chem. 2016, 12, 2450–2456, doi:10.3762/bjoc.12.238

• Nikolay O. Chalkov Vladimir K. Cherkasov Gleb A. Abakumov Andrey G. Starikov Viacheslav A. Kuropatov Laboratory of Organoelement Compounds, G.A. Razuvaev Institute of Organometallic Chemistry of RAS, 603950, GSP-445, Tropinina str., 49, Nizhny Novgorod, Russia N. I. Lobachevsky Nizhny Novgorod

Useful access to enantiomerically pure protected inositols from carbohydrates: the aldohexos-5-uloses route

• Felicia D’Andrea,
• Giorgio Catelani,
• Lorenzo Guazzelli and
• Venerando Pistarà

Beilstein J. Org. Chem. 2016, 12, 2343–2350, doi:10.3762/bjoc.12.227

• ][20][21], by microbial oxidation; 3) carbocyclization involving organometallic intermediates (Ferrier II reaction [22] performed on 6-O-acyl-hex-5-enopyranosides followed by reduction [23][24]; trialkylaluminium [25][26] or titanium(IV)-assisted [27] conversion of hex-5-enopyranosides and SmI2

Organometallic chemistry

• Bernd F. Straub,
• Rolf Gleiter,
• Claudia Meier and
• Lutz H. Gade

Beilstein J. Org. Chem. 2016, 12, 2216–2221, doi:10.3762/bjoc.12.213

• -Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany 10.3762/bjoc.12.213 This Thematic Series is dedicated to the memory of Professor Peter Hofmann (Figure 1) whose research work included many seminal contributions to the field of organometallic chemistry [1][2

• ][3]. Organometallic chemistry has therefore been chosen as the topic of this Thematic Series of the Beilstein Journal of Organic Chemistry. Over a period of many decades, the chemistry of metal–carbon bonds has given rise to an ever-growing field of fundamental research and applied science, merging

• the reactivity of inorganic complexes with the structural diversity of organic compounds. The contributions in this Thematic Series reflect the broad impact of organometallic compounds in various fields of modern chemical research. These include the tailoring of new ancillary ligands, the

Regiocontroled Pd-catalysed C5-arylation of 3-substituted thiophene derivatives using a bromo-substituent as blocking group

• Mariem Brahim,
• Hamed Ben Ammar,
• Jean-François Soulé and
• Henri Doucet

Beilstein J. Org. Chem. 2016, 12, 2197–2203, doi:10.3762/bjoc.12.210

• reactions can be performed, an organometallic compound must be synthesized. In 1990, Ohta and co-workers described the Pd-catalysed direct arylation of thiophene derivatives by coupling reaction with aryl halides [15][16]. This is a highly powerful method for a greener access to a very broad range of

• arylated thiophenes [17][18][19][20][21][22][23][24][25]. The method is very attractive in terms of green chemistry, because its major by-products are not metal salts but a base associated to HX, and synthesis of an organometallic derivative can be avoided. However, for C3-substituted thiophenes, arylation

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

• ], and iii) the conversion of oils for which lipase was identified as the most suitable enzyme for an innovative and green production of biodiesel [19]. Other catalytic systems: In addition to the above-described catalysts, amines and organometallic derivatives also find applications in the field of

From supramolecular chemistry to the nucleosome: studies in biomolecular recognition

• Marcey L. Waters

Beilstein J. Org. Chem. 2016, 12, 1863–1869, doi:10.3762/bjoc.12.175

• toward biology. On to graduate school in organometallic chemistry Once I “found” organic chemistry, the path to graduate school was relatively direct. My TA, Rich Engler, encouraged me to pursue research, and I did so, joining the group of Professor Perrin, who had engaged me in organic chemistry in the

• education! With my research experiences in physical organic chemistry and inorganic chemistry, and with the boom in organometallic research at that time, I chose to pursue mechanistic organometallic chemistry for my Ph.D. at the University of Chicago in the group of Bill Wulff. Research in the group spanned

• organometallic methodology, asymmetric catalysis, total synthesis, and mechanistic studies. I opted for the latter and spent my Ph.D. studying the mechanism of the Wulff–Dötz reaction [1], while at the same time gaining a broad background in methodology and synthesis (Figure 2). I had a fantastic time in

Cp₂TiCl/D₂O/Mn, a formidable reagent for the deuteration of organic compounds

• Antonio Rosales and
• Ignacio Rodríguez-García

Beilstein J. Org. Chem. 2016, 12, 1585–1589, doi:10.3762/bjoc.12.154

• experimental conditions and with great economic advantages. Keywords: deuteration; deuterium atom transfer; radical and/or organometallic chemistry; titanocene; Introduction Deuterium is a stable isotope of hydrogen with 0.015% natural abundance broadly used in organic chemistry, pharmacology, organometallic

• C–H bonds [8][9]. More recently, organometallic catalysts have been used in the development of methods for deuteration of organic compounds. In this sense, it has been reported that iridium complexes can catalyse the H/D exchange of arenes, cyclic alkenes and vinyl groups [10][11][12]. Ruthenium

•  1). In presence of D2O these radicals (pathway A) can be reduced into deuterated compounds. The reduction can proceed via hydrolysis of an organometallic alkyl-TiIV intermediate (Scheme 2, pathway A1) or via deuterium-atom transfer (DAT) from D2O to radicals (Scheme 2, pathway A2). In the case of

One-pot synthesis of 4′-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling

• Roman Yu. Peshkov,
• Elena V. Panteleeva,
• Wang Chunyan,
• Evgeny V. Tretyakov and
• Vitalij D. Shteingarts

Beilstein J. Org. Chem. 2016, 12, 1577–1584, doi:10.3762/bjoc.12.153

• introduction of an organometallic group is necessary. The last disadvantage is overcome to some extent by the direct C–H arylation protocols [18], but usually they are catalytic and thus the resulting cross-coupling products contain traces of transition metals difficult to remove that limits their use in areas

A T-shape diphosphinoborane palladium(0) complex

• Patrick Steinhoff and
• Michael E. Tauchert

Beilstein J. Org. Chem. 2016, 12, 1573–1576, doi:10.3762/bjoc.12.152

• between the oxidations states Pd(0)/Pd(II) is of potential interest for organometallic transformations involved in homogeneous catalysis, such as the reductive elimination. Here we report the synthesis of the diphosphinoborane (o-PCy2-C6H4)2BPh ligand CyDPBPh. CyDPBPh reacts with CpPd(η3-C3H5) yielding