(E,Z)-1,1,1,4,4,4-Hexafluorobut-2-enes: hydrofluoroolefins halogenation/dehydrohalogenation cascade to reach new fluorinated allene

• Nataliia V. Kirij,
• Andrey A. Filatov,
• Yurii L. Yagupolskii,
• Sheng Peng and
• Lee Sprague

Beilstein J. Org. Chem. 2024, 20, 452–459, doi:10.3762/bjoc.20.40

• defluorosilylation product was obtained [11]. In a related study of the hydrosilylation reaction of olefins 1a,b, it was shown that, depending on the catalyst used, platinum or rhodium compounds, along with the products of the addition of silane to the double bond, the elimination of the fluorine atom occurs with

• isolated in a pure state. For iodoolefin 7a, we found an alternative route for its synthesis. We have previously shown that hydrosilylation reaction of hexafluorobut-2-yne with triethylsilanes gave (E)-1,1,1,4,4,4-hexafluoro-2-triethylsilylbut-2-ene (8) [23]. Going back to the study of the obtained silane

Radical chemistry in polymer science: an overview and recent advances

• Zixiao Wang,
• Feichen Cui,
• Yang Sui and
• Jiajun Yan

Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116

• . Cook et al. [85] presented the first report of volumetric additive manufacturing-printed thiol–ene resins and showed the potential of the thiol–ene system. In addition to thiol–ene chemistry, radical hydrosilylation was also used to prepare linear, branched, or cross-linked polymers via a step-growth

• , and monomers [127][128][129]. Polysiloxanes are another class of crosslinkable polymers. Modern silicone industry typically uses Pt-catalyzed hydrosilylation to crosslink multi-vinyl polysiloxane with silicon hydride compounds to manufacture silicone rubbers [130]. However, hydrosilylation may also be

• achieved via a radical mechanism (Scheme 17). In comparison to the Pt-catalyzed system, the radical-induced hydrosilylation has a lower cost, better tolerance to coordinating functionalities, and yields products without metal residues, but its efficiency is inferior to transition-metal catalyzed methods

Application of N-heterocyclic carbene–Cu(I) complexes as catalysts in organic synthesis: a review

• Nosheen Beig,
• Varsha Goyal and
• Raj K. Bansal

Beilstein J. Org. Chem. 2023, 19, 1408–1442, doi:10.3762/bjoc.19.102

• diversity, low cost, and versatile applications. This article overviews applications of NHC–Cu(I) complexes as catalysts in organic synthesis over the last 12 years, which include hydrosilylation reactions, conjugate addition, [3 + 2] cycloaddition, A3 reaction, boration and hydroboration, N–H and C(sp2)–H

• addition; [3 + 2] cycloaddition reaction; hydrosilylation reaction; N-heterocyclic carbenes; NHC–Cu complexes; NHC–Cu complexes as catalyst; Introduction N-Heterocyclic carbenes (NHCs) are a neutral species having the carbene carbon atom as a part of the nitrogen heterocyclic ring. The transient

• catalysts for hydrosilylation and [3 + 2] cycloaddition discussed later [39]. 1.4 By ligand displacement Corrigan and co-worker stabilized homoleptic copper- and silver bis(trimethylsilyl)phosphido compounds [M6{P(SiMe3)2}6] (M = Cu, Ag) through their coordination with NHC ligands. For this purpose, they

Friedel–Crafts acylation of benzene derivatives in tunable aryl alkyl ionic liquids (TAAILs)

• Swantje Lerch,
• Stefan Fritsch and
• Thomas Strassner

Beilstein J. Org. Chem. 2023, 19, 212–216, doi:10.3762/bjoc.19.20

• proved to be a potent reaction medium in catalytic hydrosilylation [53], hydroamination and hydroarylation [54], as well as for the synthesis of nanoparticles [55][56]. Results and Discussion Ionic liquids 1–6 were synthesized via a three-step procedure starting from commercially available aniline

On the application of 3d metals for C–H activation toward bioactive compounds: The key step for the synthesis of silver bullets

• Renato L. Carvalho,
• Amanda S. de Miranda,
• Mateus P. Nunes,
• Roberto S. Gomes,
• Guilherme A. M. Jardim and
• Eufrânio N. da Silva Júnior

Beilstein J. Org. Chem. 2021, 17, 1849–1938, doi:10.3762/bjoc.17.126

• described the dehydrosilylation and hydrosilylation of alkenes to afford silylated alkanes and alkenes in excellent yields and stereoselectivity, depending on the phosphine-based ligand employed. The reaction proved to work through a redox-neutral path, being considered an atom-economical process

Valorisation of plastic waste via metal-catalysed depolymerisation

• Francesca Liguori,
• Carmen Moreno-Marrodán and
• Pierluigi Barbaro

Beilstein J. Org. Chem. 2021, 17, 589–621, doi:10.3762/bjoc.17.53

• depolymerisation of PET flakes from various sources (water bottles, dyed soda bottles, pillow filling, yoghurt pots). However, the role of HNTf2 was unclear. In a different approach, hydrogenolysis-like depolymerisation was achieved through a hydrosilylation strategy, using the pincer Ir(III) complex [Ir(POCOP)H

Synthetic approaches to bowl-shaped π-conjugated sumanene and its congeners

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 2212–2259, doi:10.3762/bjoc.16.186

• strategy via the transfer of sp3 chirality of 27 into the bowl chirality of 28 as a key conversion (Scheme 3) [17][31]. In this context, they began with the Pd-catalyzed hydrosilylation reaction using HSiCl3 at −3 °C in the presence of a chiral phosphine ligand to furnish the hydrosilylated product which

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

• , including both diazoesters and diazoketones as carbene precursors. After the impressive report from Dow Corning on the hydrosilylation of alkenes in 2013 [78], recently, the Buchwald group extended this chemistry to the asymmetric hydrosilylation of alkenes [79]. They used nonracemic ligand (S,S)-Ph-BPE

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

• , recyclable catalyst in the N-arylation of indoles [45][46]. Copper catalysts have shown exceptional enantioselectivity for reactions such as hydrosilylation, hydroboration, and heterogeneous as well as homogeneous hydrogenation [47][48][49]. Also, the copper salts found used as oxidants in a number of

• ][60]. They have been employed for a number of organic reactions viz., hydrosilylation of aldehydes and ketones, acetylation reactions, redox reactions, oxidative esterification, etc. [61][62][63]. Thus, in concern with increasing demand for sustainable development, a growing number of catalytic

Application of olefin metathesis in the synthesis of functionalized polyhedral oligomeric silsesquioxanes (POSS) and POSS-containing polymeric materials

• Patrycja Żak and
• Cezary Pietraszuk

Beilstein J. Org. Chem. 2019, 15, 310–332, doi:10.3762/bjoc.15.28

• chemistry), POSS are often functionalized through the chemical processes of C=C bond transformation, e.g., hydrosilylation, Heck coupling, silylative coupling and olefin metathesis. Olefin metathesis, i.e., catalytic exchange of double bonds between carbon atoms, is a powerful tool in organic synthesis. The

Glycosylation reactions mediated by hypervalent iodine: application to the synthesis of nucleosides and carbohydrates

• Yuichi Yoshimura,
• Hideaki Wakamatsu,
• Yoshihiro Natori,
• Yukako Saito and
• Noriaki Minakawa

Beilstein J. Org. Chem. 2018, 14, 1595–1618, doi:10.3762/bjoc.14.137

• nucleobase by using a combination of hypervalent iodine and an appropriate Lewis acid (Figure 4). As shown in Scheme 12, an oxidative coupling reaction was examined using a model reaction [63]. Cycloalkenylsilanes 89a,b and 90a,b were prepared by hydrosilylation of cyclopentadiene and cyclohexadiene. Using

Synthesis of substituted Z-styrenes by Hiyama-type coupling of oxasilacycloalkenes: application to the synthesis of a 1-benzoxocane

• James R. Vyvyan,
• Courtney A. Engles,
• Scott L. Bray,
• Erik D. Wold,
• Christopher L. Porter and
• Mikhail O. Konev

Beilstein J. Org. Chem. 2017, 13, 2122–2127, doi:10.3762/bjoc.13.209

• -hydrosilylation of alkynols. One of the cross-coupling products was converted to a 1-benzoxocane, albeit in low yield, using an intramolecular Buchwald–Hartwig etherification. The cyclic ether produced contains the carbon skeleton of heliannuol A. Keywords: cross-coupling; heterocycles; hydrosilylation

• ] and oxasilacycloalkenes (cyclic siloxanes, cf. Figure 1) [6][7][8] is an excellent method to prepare stereodefined alkenes. The cyclic siloxanes can be prepared in a number of ways: hydrosilylation of alkynes [11][12][13], semihydrogenation of silyl alkynes [14], ring-closing metathesis (RCM) [15][16

• . Results and Discussion The oxasilacycloalkenes used in this study were readily prepared by intramolecular anti-hydrosilylation of alkynols 5–7 using the method reported by Ball and Trost (Scheme 1) [12][13]. Alkynol 5 was commercially available, 6 was readily prepared following literature procedures (see

Phenylsilane as an effective desulfinylation reagent

• Wanda H. Midura,
• Aneta Rzewnicka and
• Jerzy A. Krysiak

Beilstein J. Org. Chem. 2017, 13, 1513–1517, doi:10.3762/bjoc.13.150

• another convenient method for the reduction of carbonyl compounds, although low selectivities have sometimes been observed and the reaction usually required drastic conditions [9]. Also, the catalytic hydrosilylation of carbonyl moieties has become an important transformation as an alternative reduction

• methodology [10][11][12][13][14]. Besides the well-known metal-catalyzed hydrosilylation, transition metals in the presence of Brønsted or Lewis acids were used for the reduction. Recently base-activated silanes were also used for this purpose [15][16][17]. Results and Discussion Our recent investigations

• therefore a subject of our interest. To extend the investigations on the reduction of esters using a reagent with tolerance for other functional groups present in the structure, we applied a hydrosilylation methodology (Scheme 1). Various cyclopropyl phosphonates were subjected to the reaction with an

Synthesis, structure, and mechanical properties of silica nanocomposite polyrotaxane gels

• Kazuaki Kato,
• Daisuke Matsui,
• Koichi Mayumi and
• Kohzo Ito

Beilstein J. Org. Chem. 2015, 11, 2194–2201, doi:10.3762/bjoc.11.238

• reactions between triethoxysilyl groups during hydrosilylation. Since the pure TES-PR DMSO solution was stable at room temperature, the solution was used for the following reaction with silica nanoparticles. A TES-PR solution in DMSO was mixed with a dispersed solution of silica nanoparticles with 15 nm

Half-sandwich nickel(II) complexes bearing 1,3-di(cycloalkyl)imidazol-2-ylidene ligands

• Johnathon Yau,
• Kaarel E. Hunt,
• Laura McDougall,
• Alan R. Kennedy and
• David J. Nelson

Beilstein J. Org. Chem. 2015, 11, 2171–2178, doi:10.3762/bjoc.11.235

• ketone α-arylation [3][13]. These species can also catalyse hydrosilylation reactions [14]. Chatani and co-workers have recently reported that ICy (ICy = 1,3-dicyclohexylimidazol-2-ylidene) is a superior ligand for the cross-coupling of aryl and benzyl methyl ethers with arylboronic acid esters, when

A carbohydrate approach for the formal total synthesis of (−)-aspergillide C

• Pabbaraja Srihari,
• Namballa Hari Krishna,
• Ydhyam Sridhar and
• Ahmed Kamal

Beilstein J. Org. Chem. 2014, 10, 3122–3126, doi:10.3762/bjoc.10.329

• , utilizing a Trost hydrosilylation and protodesilylation as key reactions. Keywords: alkynylation; chiron approach; Ferrier-type C-glycosylation; macrolide; Introduction Aspergillides A, B and C (Figure 1) (three, novel, bicyclic, 14-membered macrolides with 2,6-cis or trans-fused di- or tetrahydropyan

• , the stage was set to proceed further for the partial reduction of the alkyne moiety to obtain the trans-configured olefin. Based on our previous experience with this transformation, we proceeded directly with Trost’s hydrosilylation–protodesilylation protocol [32], where alkyne 11 was treated with

• tri-O-acetyl-D-galactal. A C-glycosidation, Trost’s hydrosilylation and protodesilylation protocol have been used as the key steps for achieving the formal total synthesis. Structures of aspergillides. Key NOESY correlations observed in compound 11. Retrosynthetic analysis for (−)-aspergillide C

Linear-g-hyperbranched and cyclodextrin-based amphiphilic block copolymer as a multifunctional nanocarrier

• Yamei Zhao,
• Wei Tian,
• Guang Yang and
• Xiaodong Fan

Beilstein J. Org. Chem. 2014, 10, 2696–2703, doi:10.3762/bjoc.10.284

• achieve controlled drug release. An amphiphilic, triblock polymer (ABC) with hyperbranched polycarbonsilane (HBPCSi) and β-cyclodextrin (β-CD) moieties were first synthesized by the combination of a two-step reversible addition-fragmentation transfer polymerization into a pseudo-one-step hydrosilylation

• chain of two PHEMA blocks via a pseudo-one-step hydrosilylation reaction. Finally, modified β-CD monomers were bonded to the amino groups of PDMAEMA block side chain by the action of ionic bonds (P3). The P3 self-assembled into stable micelles with a core–shell structure in aqueous solution. The

• laser light scattering (SEC/MALLS) results (Supporting Information File 1, Table S1 and Figure S4). Obviously, the ratio of chain length of PDMAEMA to PHEMA, 5:1, was high. The synthesis of P2 was then obtained via a pseudo-one-step hydrosilylation reaction (Supporting Information File 1, Scheme S2

Advancements in the mechanistic understanding of the copper-catalyzed azide–alkyne cycloaddition

• Regina Berg and
• Bernd F. Straub

Beilstein J. Org. Chem. 2013, 9, 2715–2750, doi:10.3762/bjoc.9.308

• or PF6) as catalysts for hydrosilylation reactions of aldehydes, ketones and esters [151][152]. These complexes also display very high catalytic activity in CuAAC reactions in water (Table 3), under neat conditions or as homogeneous catalysts in acetonitrile solution [153]. [(ICy)2Cu]PF6 turned out

Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydes

• Kegong Ji,
• Jonathan Nelson and
• Liming Zhang

Beilstein J. Org. Chem. 2013, 9, 1925–1930, doi:10.3762/bjoc.9.227

• alkyne end (Figure 2). This revelation is consistent with the 13C NMR chemical shifts of the alkynyl carbons. The observed regioselectivity can be ascribed to a selective attack of the nucleophilic oxidant to the more electrophilic distal C(sp). Notably, a recently published Pt-catalyzed hydrosilylation

Linkage of α-cyclodextrin-terminated poly(dimethylsiloxanes) by inclusion of quasi bifunctional ferrocene

• Helmut Ritter,
• Berit Knudsen and
• Valerij Durnev

Beilstein J. Org. Chem. 2013, 9, 1278–1284, doi:10.3762/bjoc.9.144

• -terminated poly(dimethylsiloxanes) to create novel supramolecular linear or macrocyclic siloxan structures based on double inclusion complexes with ferrocene. Results and Discussion The syntheses of α-CD-terminated poly(dimethylsiloxanes) 4 and 5 were performed by hydrosilylation of mono-((6-N-allylamino)-6

• ). The disappearance of the absorption bands at 2100 cm−1 clearly shows the successful hydrosilylation of the educts to the newly synthesized derivatives 4 and 5. The 1H NMR spectra of the α-CD-functionalized poly(dimethylsiloxanes) (α-CD-DS 4 and α-CD-PDMS 5) reveal the characteristic signals of the Si

• α-CD-disiloxane 4 (A) (dashed line) and the supramolecular formation of α-CD-disiloxane 4 with ferrocene (B) (solid line). Hydrosilylation of Si–H terminated poly(dimethylsiloxanes) 1 and 2 with mono-((6-N-(allylamino)-6-deoxy)-peracetylated-α-CD (3) to compounds 4 (n = 1) and 5 (n = 6–37

De novo synthesis of D- and L-fucosamine containing disaccharides

• Daniele Leonori and
• Peter H. Seeberger

Beilstein J. Org. Chem. 2013, 9, 332–341, doi:10.3762/bjoc.9.38

• commercial sources. Inspired by the work from the Trost group [54][55], an alternative reduction protocol based on a Ru-catalyzed hydrosilylation–protodesilylation sequence was pursued (Scheme 2B). Thus, exposure of alkyne 2 to Cp*Ru(CH3CN)3PF6 catalyst in the presence of the appropriate trialkylsilane gave

• - and L-fucosamine building blocks. (A) Synthesis of aldehydes 6a and 6b. (B) Alkyne reduction by hydrosilylation–protodesilylation sequence (see Table 1). Synthesis of D-fucosamine building blocks 8a and 8b. Epimerization of aldehyde 6a. Synthesis of L-fucosamine building block L-8a from D-Garner

• aldehyde. Synthesis of D- and L-fucosamine-containing mono- and disaccharides carrying the pentanolamine linker. Hydrosilylation yields. Oxidation of 5a to D-fucosamine D-8a. Supporting Information Supporting Information File 72: 1H NMR, COSY, 13C NMR and HSQC spectra and the crystallographic data file

Iron-containing mesoporous aluminosilicate catalyzed direct alkenylation of phenols: Facile synthesis of 1,1-diarylalkenes

• Satyajit Haldar and
• Subratanath Koner

Beilstein J. Org. Chem. 2013, 9, 49–55, doi:10.3762/bjoc.9.6

• ]. Furthermore, a variety of available reactions to functionalize the double bond, such as reductive (hydrogenation, hydrosilylation, etc.), oxidative (epoxidation, halogenations, dihydroxylation, etc.) or cycloaddition transformations, encourage such vinylation process as an attractive primary tool in organic

Olefin metathesis in nano-sized systems

• Didier Astruc,
• Abdou K. Diallo,
• Sylvain Gatard,
• Liyuan Liang,
• Cátia Ornelas,
• Victor Martinez,
• Denise Méry and
• Jaime Ruiz

Beilstein J. Org. Chem. 2011, 7, 94–103, doi:10.3762/bjoc.7.13

• performing RCM of branches and then to remove the core has also been applied by the Peng group to produce nanoparticle-cored dendrimers [48][49][50][51]. Dendrimers have been synthesized by reaction sequences involving hydrosilylation of olefin-terminated dendrimer cores followed by Williamson reactions with

• dendritic core containing 9 allyl termini after two iterative metathesis-hydrosilylation reactions (Scheme 6). This principle has also been extended to polymers and gold nanoparticles [54]. Dendrimer-induced olefin metathesis in water Olefin metathesis of hydrophobic substrates, which are the large majority

Concise methods for the synthesis of chiral polyoxazolines and their application in asymmetric hydrosilylation

• Wei Jie Li,
• Zun Le Xu and
• Sheng Xiang Qiu

Beilstein J. Org. Chem. 2010, 6, No. 29, doi:10.3762/bjoc.6.29

• concomitant removal of water or the alcohol produced in the reaction. The method is much simpler and more efficient in comparison to those methods reported in the literature. The compounds were used as chiral ligands in the rhodium-catalyzed asymmetric hydrosilylation of aromatic ketones, and the effects of

• the linkers and the substituents present on the oxazoline rings on the yield and enantioselectivity investigated. Compound 2 was identified as the best ligand of this family for the hydrosilylation of aromatic ketones. Keywords: aromatic ketone; hydrosilylation; polyoxazoline; rhodium; synthesis

• the preparation of novel chiral polyoxazoline ligands (Figure 1). These processes are high yield reactions with simple workup procedures. Furthermore, we have also investigated the reactivities and resulting enantioselectivities of the newly synthesized ligands in the asymmetric hydrosilylation

Enantioselective synthesis of tricyclic amino acid derivatives based on a rigid 4-azatricyclo[5.2.1.0^2,6]decane skeleton

• Matthias Breuning,
• Tobias Häuser,
• Christian Mehler,
• Christian Däschlein,
• Carsten Strohmann,
• Andreas Oechsner and
• Holger Braunschweig

Beilstein J. Org. Chem. 2009, 5, No. 81, doi:10.3762/bjoc.5.81

• of 11 delivered the exo-configured alcohol rac-12, which was oxidized with PCC furnishing rac-9 in 79% yield. The asymmetric synthesis of the ketone 9 was realized by enantioselective hydration of the meso-alkene 11 using Hayashi’s method (Scheme 2) [25][26][27][28][29][30]: Hydrosilylation with

• and 8 were successfully accomplished in 9–10 steps starting with inexpensive endo-carbic anhydride (10). The key stereochemical step was the desymmetrization of the meso-alkene 11 using Hayashi’s hydrosilylation/oxidation procedure, which provided the endo-alcohol 12 in 85% ee. The target molecules

• the racemic ketone rac-9. i) NH4OAc, HOAc, Δ, 4 d, 100%; ii) LiAlH4, THF, Δ, 1 d, 87% [24]; iii) Boc2O, CH2Cl2, rt, 16 h, 85%; iv) NaBH4, Me2SO4, THF, rt, 6 h, then NaOH, H2O2, Δ, 90 min, 75%; v) PCC, Celite®, CH2Cl2, rt, 16 h, 79%. Enantioselective hydrosilylation/oxidation of 11. i) HSiCl3, [Pd(C3H5