Palladium-catalyzed ring-opening reactions of cyclopropanated 7-oxabenzonorbornadiene with alcohols

• Katrina Tait,
• Oday Alrifai,
• Rebecca Boutin,
• Jamie Haner and
• William Tam

Beilstein J. Org. Chem. 2016, 12, 2189–2196, doi:10.3762/bjoc.12.209

• unsuccessful, palladium(II) catalysts in the absence of a triphenylphosphine ligand were more promising (Table 1, entries 6–9). The palladium(II) catalyst PdCl2(CH3CN)2 generated a high yield of substituted naphthalene 11a after only 24 hours and was chosen to further optimize reaction conditions. When the

• catalyst equivalency was investigated, lowering the catalyst from 10 mol % to 5 mol % reduced the yield from 89% to 27% (Table 1, entry 10) while further reducing the catalyst equivalency to 2 mol % showed no reaction (Table 1, entry 11). To confirm that the presence of a triphenylphosphine ligand would

• result in no reaction, the optimized catalyst was used with an external source of triphenylphosphine, which resulted in no reaction (Table 1, entry 12). To expand the scope of catalyst, the effect of using a platinum catalyst was investigated. The use of a platinum(IV) catalyst resulted in no reaction

Synthesis and characterization of fluorinated azadipyrromethene complexes as acceptors for organic photovoltaics

• Forrest S. Etheridge,
• Roshan J. Fernando,
• Sandra Pejić,
• Matthias Zeller and
• Geneviève Sauvé

Beilstein J. Org. Chem. 2016, 12, 1925–1938, doi:10.3762/bjoc.12.182

• (Aldrich), 4-ethynyl-α,α,α-trifluorotoluene (Aldrich), n-butyllithium solution (Aldrich), tributyltin chloride (Fisher), tributyl(phenylethynyl)tin (Aldrich), tetrakis(triphenylphosphine)palladium(0) (Aldrich), n-iodosuccinimide (abbreviated NIS, Aldrich) were used as received. All other reagents and

A flow reactor setup for photochemistry of biphasic gas/liquid reactions

• Josef Schachtner,
• Patrick Bayer and
• Axel Jacobi von Wangelin

Beilstein J. Org. Chem. 2016, 12, 1798–1811, doi:10.3762/bjoc.12.170

• convenience, reductive work-up with triphenylphosphine (PPh3) was performed to obtain the stable allyl alcohol derivative 3a which offers ample opportunities for chemical manipulations at the alcohol, alkene, and carboxamide functions. The choice of solvent is crucial as it determines the solubility of the

TMSBr-mediated solvent- and work-up-free synthesis of α-2-deoxyglycosides from glycals

• Mei-Yuan Hsu,
• Yi-Pei Liu,
• Sarah Lam,
• Su-Ching Lin and
• Cheng-Chung Wang

Beilstein J. Org. Chem. 2016, 12, 1758–1764, doi:10.3762/bjoc.12.164

• conditions in good to excellent yields. In addition, with triphenylphosphine oxide as an additive, the TMSBr-mediated direct glycosylations of glycals with a large range of alcohols were highly α-selective. Keywords: 2-deoxyglycosides; glycals; trimethylsilyl bromide (TMSBr); triphenylphosphine oxide (TPPO

Rearrangements of organic peroxides and related processes

• Ivan A. Yaremenko,
• Vera A. Vil’,
• Dmitry V. Demchuk and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162

• product, which rearranges into dioxetane 198 at 28 °C in CCl4 within 13 h. Compounds 198 can be further transformed into keto esters 199 by treatment for 24 h with triphenylphosphine in CCl4 or concentrated HCl in CCl4. When compound 197 is heated at 70 °C its rearrangement into 199 occurs very rapidly

Flow carbonylation of sterically hindered ortho-substituted iodoarenes

• Carl J. Mallia,
• Gary C. Walter and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2016, 12, 1503–1511, doi:10.3762/bjoc.12.147

• synthesis of ortho-substituted carboxylic acids, using carbon monoxide gas, has been studied for a number of substrates. The optimised conditions make use of a simple catalyst system compromising of triphenylphosphine as the ligand and palladium acetate as the pre-catalyst. Carbon monoxide was introduced

• -substituent directly over an axial site (Figure 1). The ortho-substituent therefore acts as a steric buttress hindering the approach of the incoming carbon monoxide thus slowing down the rate of the reaction. An X-ray structure of trans-bromo(o-tolyl)bis(triphenylphosphine)palladium(II) complex was reported

• -Phos (8) and triphenylphosphine (6) (Table 1, entries 2 and 5), with the difference between the conversion and the isolated yield mainly equating to the dehalogenated product namely, chlorobenzene. Next changing the amount of triethylamine used from 1.1 equiv to 1.6 equiv and 2.0 equiv, respectively

Application of Cu(I)-catalyzed azide–alkyne cycloaddition for the design and synthesis of sequence specific probes targeting double-stranded DNA

• Svetlana V. Vasilyeva,
• Vyacheslav V. Filichev and
• Alexandre S. Boutorine

Beilstein J. Org. Chem. 2016, 12, 1348–1360, doi:10.3762/bjoc.12.128

• Supporting Information File 1). This phenomenon has been already observed [24], though with quite low yields of products. These DNA derivatives were identified as products of incomplete departure of the oxidized triphenylphosphine moiety with the formation of the residue X covalently attached to the

Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization

• Barry M. Trost,
• Michael C. Ryan and
• Meera Rao

Beilstein J. Org. Chem. 2016, 12, 1136–1152, doi:10.3762/bjoc.12.110

• synthetic sequence of p-anisyl catalyst 1. In situ reduction of 4-methoxysulfonyl chloride by triphenylphosphine and trapping with (−)-menthol affords diastereomerically pure sulfinate ester 2 after enrichment by recrystallization [45]. Grignard addition attaches a TMS-protected alkyne of appropriate tether

• conversion by proton NMR. As seen in Table 4, when this experiment is performed with 3 mol % complex 1, a 54% conversion is observed after 1.5 hours (entry 1). When the same experiment is conducted with 3 mol % of CpRu(MeCN)3PF6 and 3 mol % triphenylphosphine, the reaction only proceeds to 15% conversion

Synthesis of a deuterated probe for the confocal Raman microscopy imaging of squalenoyl nanomedicines

• Eric Buchy,
• Branko Vukosavljevic,
• Maike Windbergs,
• Dunja Sobot,
• Camille Dejean,
• Simona Mura,
• Patrick Couvreur and
• Didier Desmaële

Beilstein J. Org. Chem. 2016, 12, 1127–1135, doi:10.3762/bjoc.12.109

• -bromopropane-d7 (8) with triphenylphosphine [29]. To our surprise, condensation of dialdehyde 5 with one equivalent of the ylide 4 (9, n-BuLi, THF, −78 °C) did not afford any amount of the desired deuterated olefin but only polar material that could not be characterized. In an attempt to find more efficient

Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate

• Sean P. Bew,
• Glyn D. Hiatt-Gipson,
• Graham P. Mills and
• Claire E. Reeves

Beilstein J. Org. Chem. 2016, 12, 1081–1095, doi:10.3762/bjoc.12.103

• , the synthesis of either (E)-3-methyl-4-chlorobut-2-en-1-ol ((E)-60) or (Z)-3-methyl-4-chlorobut-2-en-1-ol ((Z)-61, Scheme 8). Reacting triphenylphosphine with 1-((2-bromoethoxy)methyl)-4-methoxybenzene (55) generated non-stabilized phosphonium ylide (2-(4-methoxybenzyloxy)ethyl)triphenylphosphonium

Unconventional application of the Mitsunobu reaction: Selective flavonolignan dehydration yielding hydnocarpins

• Guozheng Huang,
• Simon Schramm,
• Jörg Heilmann,
• David Biedermann,
• Vladimír Křen and
• Michael Decker

Beilstein J. Org. Chem. 2016, 12, 662–669, doi:10.3762/bjoc.12.66

• , triphenylphosphine (Ph3P) and diethyl azodicarboxylate (DEAD) [9], versus addition of diisopropyl azodicarboxylate (DIAD) to the mixture of silibinin, acid and Ph3P [10]. In both cases, the desired C-23 ester was obtained in moderate yields, and we observed a side reaction, which we expected to be a dehydration

• Mitsunobu reaction represents a powerful method to convert primary and secondary alcohols into ester but also into various derivatives. The mechanism is well described and includes the formation of the triphenylphosphine–DIAD adduct, which then activates the alcohol making it a good leaving group

Hydroquinone–pyrrole dyads with varied linkers

• Hao Huang,
• Christoffer Karlsson,
• Maria Strømme,
• Martin Sjödin and
• Adolf Gogoll

Beilstein J. Org. Chem. 2016, 12, 89–96, doi:10.3762/bjoc.12.10

• material, a Wittig reaction was chosen as an alternative. The Wittig reaction approach is shown in Scheme 2. In this reaction, phosphonium salt 7 was prepared in quantitative yield from 5 and triphenylphosphine by reflux in toluene, according to a procedure reported for dimethoxybenzyl chloride [21]. The

Pyridylidene ligand facilitates gold-catalyzed oxidative C–H arylation of heterocycles

• Kazuhiro Hata,
• Hideto Ito,
• Yasutomo Segawa and
• Kenichiro Itami

Beilstein J. Org. Chem. 2015, 11, 2737–2746, doi:10.3762/bjoc.11.295

• strongest electron-donating N-heterocyclic carbenes, resulted in the rate acceleration of the C–H arylation reaction of heterocycles over conventional ligands such as triphenylphosphine and a classical N-heterocyclic carbene. In situ observation and isolation of the 2-pyridylidene-gold(III) species, as well

• such oxidative reaction conditions. For example, triphenylphosphine is easily oxidized to triphenylphosphine oxide by a hypervalent iodine reagent that has been used as an oxidant for gold-catalyzed C–H arylation [69]. Appropriate ligands that are tolerant to the oxidative conditions would offer

• reactions, we hypothesize that the highly electron-donating PyC ligand facilitates the oxidation of gold(I) to gold(III). As triphenylphosphine is known to be easily oxidized to triphenylphosphine oxide under the current oxidative conditions, the ligand-free gold(III) species is thought to be an active

Synthesis and photophysical characteristics of polyfluorene polyrotaxanes

• Aurica Farcas,
• Giulia Tregnago,
• Ana-Maria Resmerita,
• Pierre-Henri Aubert and
• Franco Cacialli

Beilstein J. Org. Chem. 2015, 11, 2677–2688, doi:10.3762/bjoc.11.288

• the generation of active layers in organic electronic devices. Experimental Materials and methods 1, 2, tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4], β- and γCD, bromobenzene (Br–Ph), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and quinine sulfate dehydrate in 0.5 M sulfuric acid were

Versatile synthesis and biological evaluation of novel 3’-fluorinated purine nucleosides

• Hang Ren,
• Haoyun An,
• Paul J. Hatala,
• William C. Stevens Jr,
• Jingchao Tao and
• Baicheng He

Beilstein J. Org. Chem. 2015, 11, 2509–2520, doi:10.3762/bjoc.11.272

• and Suzuki reaction conditions. To this end, 2-(tributylstannyl)furan was coupled with 6-chloropurine nucleoside 26 by Stille cross coupling [47][48] catalyzed by bis(triphenylphosphine)palladium(II) chloride in DMF (Method I) (Scheme 3). The resulting 6-aryl compound 30 was obtained in 91% yield and

• synthesize compounds 6–15. The 6-chloropurine intermediate 26 was coupled with 3-thienylboronic acid and phenylboronic acid catalyzed by tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) in toluene (Method II), resulting in the desired protected intermediates 31 and 32 in 56% and 52% yields, respectively

• and deprotection of 2,6-dichloropurine 42 was achieved with a saturated solution of ammonia in methanol to furnish 2-chloro-3’-deoxy-3’-fluoroadenosine (16). The 2,6-dichloro-intermediate 42 was coupled with 2-(tributylstannyl)furan catalyzed by bis(triphenylphosphine)palladium(II) chloride in DMF to

Cu(I)-catalyzed N,N’-diarylation of natural diamines and polyamines with aryl iodides

• Svetlana P. Panchenko,
• Alexei D. Averin,
• Maksim V. Anokhin,
• Olga A. Maloshitskaya and
• Irina P. Beletskaya

Beilstein J. Org. Chem. 2015, 11, 2297–2305, doi:10.3762/bjoc.11.250

• % (Table 1, entry 3). Diarylation of putrescine (2), on contrary, was more successful in the presence of the CuI/L1/EtCN catalytic system (Table 1, entry 4), and a similar result was obtained when using L2 together with Ph3P (Table 1, entry 6), while employing L1 with triphenylphosphine led to a low

• (Table 2, entry 7). The same catalytic system with or without triphenylphosphine was not efficient in the coupling with 4-iodobiphenyl, however, the use of L1 gave rise to the target diaryl derivative 19 in a moderate yield (Table 2, entry 8). On contrary, application of the ligand L2 was more successful

Synthesis of D-fructose-derived spirocyclic 2-substituted-2-oxazoline ribosides

• Madhuri Vangala and
• Ganesh P. Shinde

Beilstein J. Org. Chem. 2015, 11, 2289–2296, doi:10.3762/bjoc.11.249

• glycosyl azides via intramolecular condensation with a vicinal ester group in the presence of triphenylphosphine [27] or from the reaction of D-glucals with N-iodosuccinimide and amides [28][29]. Alternatively, 5 can be derived by a Ritter-like [30][31] transformation, involving trapping of the

Stereoselective synthesis of hernandulcin, peroxylippidulcine A, lippidulcines A, B and C and taste evaluation

• Marco G. Rigamonti and
• Francesco G. Gatti

Beilstein J. Org. Chem. 2015, 11, 2117–2124, doi:10.3762/bjoc.11.228

• ]. Indeed, the treatment of (–)-isopulegol with diisopropyl azodicarboxylate (DIAD) and p-nitrobenzoic acid in the presence of triphenylphosphine gave the corresponding ester in an almost quantitative yield. The latter was easily purified by crystallization from n-hexane, and then transesterificated with

• -up followed by treatment of the reaction mixture with triphenylphosphine, the unreacted lippidulcines B and C were oxidized with MnO2 to give ketone 14 together to the unreacted O-TMS protected lippidulcine A, 15a ([α]D −11.3° (c 1.0, CHCl3)). The latter were easily separated by column chromatography

A new approach to ferrocene derived alkenes via copper-catalyzed olefination

• Vasily M. Muzalevskiy,
• Aleksei V. Shastin,
• Alexandra D. Demidovich,
• Namiq G. Shikhaliev,
• Abel M. Magerramov,
• Victor N. Khrustalev,
• Rustem D. Rakhimov,
• Sergey Z. Vatsadze and
• Valentine G. Nenajdenko

Beilstein J. Org. Chem. 2015, 11, 2072–2078, doi:10.3762/bjoc.11.223

• –Fuchs reaction) using a 2–4-fold molar excess of triphenylphosphine [27][28][29][30][31]. Results and Discussion Synthesis of halovinylferrocenes A few years ago we discovered a new reaction for a double carbon–carbon bond formation – the reaction of catalytic olefination. It was shown that the copper

Investigation on the reactivity of α-azidochalcones with carboxylic acids: Formation of α-amido-1,3-diketones and highly substituted 2-(trifluoromethyl)oxazoles

• Kandasamy Rajaguru,
• Arumugam Mariappan,
• Rajendran Suresh,
• Periasamy Manivannan and
• Shanmugam Muthusubramanian

Beilstein J. Org. Chem. 2015, 11, 2021–2028, doi:10.3762/bjoc.11.219

• . This is illustrated with one reaction in which 3 was subjected to treatment with triphenylphosphine in the presence of iodine and triethylamine in dry dichloromethane at room temperature (Scheme 4) [34][35]. As expected, compounds 3 are converted to 2,4,5-substituted oxazole 7 regiospecifically in good

• allowing the reaction mixture to cool to room temperature, ice-cold water was added. The precipitate obtained was filtered, dried in vacuum and recrystallized from ethanol to afford 3e (yield: 1.93 g; 88%). Synthesis of 7: To a stirred solution of triphenylphosphine (2.0 equiv) and iodine in

New aryloxybenzylidene ruthenium chelates – synthesis, reactivity and catalytic performance in ROMP

• Patrycja Żak,
• Szymon Rogalski,
• Mariusz Majchrzak,
• Maciej Kubicki and
• Cezary Pietraszuk

Beilstein J. Org. Chem. 2015, 11, 1910–1916, doi:10.3762/bjoc.11.206

• Grubbs catalysts bearing a triphenylphosphine ligand (or its para-substituted analogues) by metathesis exchange with substituted 2-vinylphenols. The complexes behave like a latent catalyst and are characterized by an improved catalytic behaviour as compared to that of the known analogues, i.e., they

• donating and electron withdrawing substituents at the benzylidene ligand in para position to the coordinating oxygen and bearing instead of a strong sigma-donor ligand – tricyclohexylphosphine a weaker sigma-donor – a triphenylphosphine ligand or its derivatives. The catalytic performance of the

• synthesized complexes were tested in ROMP of COD and a single selected norbornene derivative. Results and Discussion Synthesis Complexes containing triphenylphosphine ligands and substituted triphenylphosphine ligands were isolated in high yields (95–98%) according to the methodology described by Grubbs

Synthesis and structures of ruthenium–NHC complexes and their catalysis in hydrogen transfer reaction

• Chao Chen,
• Chunxin Lu,
• Qing Zheng,
• Shengliang Ni,
• Min Zhang and
• Wanzhi Chen

Beilstein J. Org. Chem. 2015, 11, 1786–1795, doi:10.3762/bjoc.11.194

• displaying the typical octahedral geometry. The reaction of [RuL1(CH3CN)4](PF6)2 with triphenylphosphine and 1,10-phenanthroline resulted in the substitution of one and two coordinated acetonitrile ligands and afforded [RuL1(PPh3)(CH3CN)3](PF6)2 (4) and [RuL1(phen)(CH3CN)2](PF6)2 (5), respectively. The

• complexes show good catalytic activity in the transfer hydrogenation of ketones. The reaction of acetonitrile-coordinated Ru–NHC complex 2 with other donors such as triphenylphosphine and 1,10-phenanthroline was also studied. Results and Discussion Synthesis and characterization of [Ru(L1)2(CH3CN)2](PF6)2

• triphenylphosphine and 1,10-phenanthroline The coordinated acetonitrile ligands could be easily replaced by various N- and P-donors [22]. The reactions of the acetonitrile-coordinated Ru–NHC complexes with other ligands were studied. The reaction of complex 2 with an excess of triphenylphosphine and 1,10

A new method for the synthesis of α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues

• Anna Kuźnik,
• Roman Mazurkiewicz,
• Mirosława Grymel,
• Katarzyna Zielińska,
• Jakub Adamek,
• Ewa Chmielewska,
• Marta Bochno and
• Sonia Kubica

Beilstein J. Org. Chem. 2015, 11, 1418–1424, doi:10.3762/bjoc.11.153

• too low electrophilic activity of the α-carbon atom of the removed 1-methoxyalkylphosphonic acid derivatives. However, the electrophilic activity of the latter compounds was enough for their reaction with triphenylphosphine. Therefore, to enhance the electrophilic activity of the discussed 1

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

• cyclopalladated complexes Synthesis of (S)-chloro-[(4-isopropyloxazolinyl)-2-naphthyl](triphenylphosphine)palladium(II) (5): The complex (3) was synthesized using two methods: Method A: A mixture of Pd(OAc)2 (50 mg, 0.22 mmol, 1 equiv), AcONa (18.3 mg, 0.22 mmol, 1 equiv) and (S)-4-isopropyl-2-(naphthalen-1-yl

Gold-catalyzed formation of pyrrolo- and indolo-oxazin-1-one derivatives: The key structure of some marine natural products

• Sultan Taskaya,
• Nurettin Menges and
• Metin Balci

Beilstein J. Org. Chem. 2015, 11, 897–905, doi:10.3762/bjoc.11.101

• reaction we used a palladium catalyst and a copper(I) cocatalyst in the presence of triphenylphosphine and triethylamine as the base. The carboxylic acids were then submitted to a gold-catalyzed cyclization reaction (Table 2). The optimized reaction conditions for cyclization was employed for pyrrole- and