Interactions of cyclodextrins and their derivatives with toxic organophosphorus compounds

• Sophie Letort,
• Sébastien Balieu,
• William Erb,
• Géraldine Gouhier and
• François Estour

Beilstein J. Org. Chem. 2016, 12, 204–228, doi:10.3762/bjoc.12.23

• hydrogen bonding between the secondary OH groups of the CD and the reactive site of the guest. Indeed, such interactions increase the nucleophilicity of the secondary hydroxy groups and facilitate their attack onto the phosphorus atom. Indeed, when the para-nitrophenoxy moiety is deeply included into the

Scope and limitations of the dual-gold-catalysed hydrophenoxylation of alkynes

• Adrián Gómez-Suárez,
• Yoshihiro Oonishi,
• Anthony R. Martin and
• Steven P. Nolan

Beilstein J. Org. Chem. 2016, 12, 172–178, doi:10.3762/bjoc.12.19

• nucleophilicity decreases and an increase in catalyst loading is needed in order to maintain relatively short reaction times (3ai and 3al) [31]. The steric hindrance on the phenol was studied next. Increasing it, with either allyl (3am) or tert-butyl (3an) groups on the ortho-position also required 1 mol % of

Spiro-fused carbohydrate oxazoline ligands: Synthesis and application as enantio-discrimination agents in asymmetric allylic alkylation

• Jochen Kraft,
• Martin Golkowski and
• Thomas Ziegler

Beilstein J. Org. Chem. 2016, 12, 166–171, doi:10.3762/bjoc.12.18

• ester 11 as boron source (Scheme 2) [22][23][24]. 2-Pyridineboronic acid 11 was chosen due to its increased nucleophilicity compared to other boron sources like pinacol boronic esters or MIDA boronates [25][26]. The cross coupling proceeded smoothly in THF and gave ligands 9 and 10 in good yields

Catalytic asymmetric formal synthesis of beraprost

• Yusuke Kobayashi,
• Ryuta Kuramoto and
• Yoshiji Takemoto

Beilstein J. Org. Chem. 2015, 11, 2654–2660, doi:10.3762/bjoc.11.285

• condensation followed by diazo-transfer reaction. The chiral dihydrobenzofuran scaffold (5 or 6) could be synthesized by asymmetric intramolecular oxa-Michael reaction (AIOM) of α,β-unsaturated amides 7 or 8. Such reactions are generally considered to be challenging due to low nucleophilicity of the oxygen

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

• corresponding products 16a and 17a in moderate yields. Finally, 2-cyanothiophene (Table 1, entry 13) also reacted with 5a to give 18a in 45% yield. Further, 4-nitrobenzonitrile and 2-cyanopyridine with an electron-withdrawing group or ring did not give the expected product due to the reduced nucleophilicity of

Convenient preparation of high molecular weight poly(dimethylsiloxane) using thermally latent NHC-catalysis: a structure-activity correlation

• Stefan Naumann,
• Johannes Klein,
• Dongren Wang and
• Michael R. Buchmeiser

Beilstein J. Org. Chem. 2015, 11, 2261–2266, doi:10.3762/bjoc.11.246

• , emphasizing that nucleophilicity is crucial for successful polymerization. Furthermore, it is interesting to note that the six- and seven-membered NHCs do not show any reactivity here, in spite of being very strong bases. While for a compound like 6-iPr a pKa-value of 28.2 (aqueous solution, 25 °C) was found

Beyond catalyst deactivation: cross-metathesis involving olefins containing N-heteroaromatics

• Kevin Lafaye,
• Cyril Bosset,
• Lionel Nicolas,
• Amandine Guérinot and
• Janine Cossy

Beilstein J. Org. Chem. 2015, 11, 2223–2241, doi:10.3762/bjoc.11.241

• , a deprotonation of the metallacyclobutane is hypothesized to explain the amine-induced decomposition (Table 3). Consequently, a modulation of the Brønsted basicity and/or the nucleophilicity of the amine/N-heteroaromatic present on an alkene may allow its use in metathesis reactions. Ring-closing

• examples of successful RCM involving alkenes containing N-heteroaromatics, it seems that decreasing their Brønsted basicity and/or their nucleophilicity through the introduction of suitable electron-withdrawing and/or bulky substituents may prevent the catalyst deactivation thus allowing the metathesis to

• hindrance next to the nitrogen atom could also play a role by decreasing the nucleophilicity of the nitrogen as attested by the formation of alkene 98f in a moderate 52% yield (Scheme 36). This strategy was applied to the formation of a broad variety of disubstituted olefins containing N-heteroaromatic

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

• nucleophilicity of the phosphine ligands. A strong electronic influence of the substituent in the ring of the phenoxybenzylidene ligand, in para position towards the oxygen atom, on the catalytic activity of the active form of the complexes was found. The presence of an electron-donating tert-butyl substituent

Pd(OAc)₂-catalyzed dehydrogenative C–H activation: An expedient synthesis of uracil-annulated β-carbolinones

• Biplab Mondal,
• Somjit Hazra,
• Tarun K. Panda and
• Brindaban Roy

Beilstein J. Org. Chem. 2015, 11, 1360–1366, doi:10.3762/bjoc.11.146

• mechanistic pathway that commence with electrophilic metalation at the indole C3 postion. The nucleophilicity of indole at C3 is well known [58] and a similar kind of electrophilic reaction leads to the intermediate A (Scheme 3). We believe this intermediate then undergoes a σ-bond metathesis reaction to form

Surprisingly facile CO₂ insertion into cobalt alkoxide bonds: A theoretical investigation

• Willem K. Offermans,
• Claudia Bizzarri,
• Walter Leitner and
• Thomas E. Müller

Beilstein J. Org. Chem. 2015, 11, 1340–1351, doi:10.3762/bjoc.11.144

• crystal solid-state structure reported for [CoIII(salen)(dinitrophenolate)] [49]. The distance between cobalt and the oxygen atom of the alkoxide chain was 1.9–1.94 Å, with a small yet systematic variation in dependence on the nucleophilicity of L. The more nucleophilic L was, the longer the Co–OR

• varied from 1.99 Å to 1.93 Å depending on the nucleophilicity of L: the less nucleophilic the ligand L was, the shorter the CoIII–O bond was. The carbon–oxygen bond lengths within the carbonate unit were 1.294(5) Å for C1–O3, 1.236(3) Å for C1–O4, and 1.392(11) Å for C1–O5, with only little variation in

• the cobalt–carbonate bond is stronger than the cobalt–alkoxide bond. Since the alkoxide is a stronger Lewis base than the carbonate, we calculated an increase in bond strength between the carbonate unit and cobalt center with respect to the cobalt(III)–alkoxide bond, depending on the nucleophilicity

Highly selective palladium–benzothiazole carbene-catalyzed allylation of active methylene compounds under neutral conditions

• Antonio Monopoli,
• Pietro Cotugno,
• Carlo G. Zambonin,
• Francesco Ciminale and
• Angelo Nacci

Beilstein J. Org. Chem. 2015, 11, 994–999, doi:10.3762/bjoc.11.111

• of the different behavior displayed by these two carbene ligands can be found in the different aromatic character of their (benzothiazole and imidazole) heterocyclic rings. It is well known that this feature can strongly affect the nucleophilicity of these NHC species, and ultimately can influence

An intramolecular C–N cross-coupling of β-enaminones: a simple and efficient way to precursors of some alkaloids of Galipea officinalis

• Hana Doušová,
• Radim Horák,
• Zdeňka Růžičková and
• Petr Šimůnek

Beilstein J. Org. Chem. 2015, 11, 884–892, doi:10.3762/bjoc.11.99

• be considered vinylogous amides. Hence, their nucleophilicity is lowered and enaminones can be more challenging substrates for C–N cross-coupling compared to ordinary enamines. We used 3a as the model substrate for the optimization study. The reaction conditions were surveyed from the following

Thiazole formation through a modified Gewald reaction

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

Beilstein J. Org. Chem. 2015, 11, 875–883, doi:10.3762/bjoc.11.98

• aromatic appendage shows that an electron donating group (entries 4 and 5, Table 4) gives a better yield than an electron withdrawing group (entries 6 and 7, Table 4). This is presumably due to a subtle balance between the basicity and nucleophilicity of the intermediate anion, which could in the case of

Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation

• Martin Weiser,
• Sergej Hermann,
• Alexander Penner and
• Hans-Achim Wagenknecht

Beilstein J. Org. Chem. 2015, 11, 568–575, doi:10.3762/bjoc.11.62

• of phenol, weakened the nucleophilicity for this type of reaction. Styrene (6) has an oxidation potential of 1.94 V (vs SCE) [22] and, hence, could also be oxidized by the chosen photocatalyst PDI. The corresponding photocatalytic nucleophilic additions to 6 (Table 1) yielded less of each product

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 these Michael acceptors and the low inherent nucleophilicity of the metal alkynylides. In 2010, Shibasaki and co-workers developed the asymmetric 1,4-addition of terminal alkynes to α,β-unsaturated thioamides [192]. In order to achieve this reaction, Shibasaki and co-workers used a soft Lewis acid

Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

• Tor E. Kristensen

Beilstein J. Org. Chem. 2015, 11, 446–468, doi:10.3762/bjoc.11.51

• due to the excellent nucleophilicity of this particular amine scaffold. After a disclosure containing two O-acylations of serine in CF3CO2H with propionyl chloride and butyryl chloride was discovered, more or less by chance, in the patent literature (in what was then a patent application) [49

IR and electrochemical synthesis and characterization of thin films of PEDOT grown on platinum single crystal electrodes in [EMMIM]Tf₂N ionic liquid

• Andrea P. Sandoval,
• Marco F. Suárez-Herrera and
• Juan M. Feliu

Beilstein J. Org. Chem. 2015, 11, 348–357, doi:10.3762/bjoc.11.40

• ) has shown an enhancement in stability, organization and electroactivity [12][13][14]. These characteristics are obtained mainly because of the dry medium, their wide electrochemical window, and their low nucleophilicity. Therefore, during the electrosynthesis of conducting polymers the overoxidation

Anion effect controlling the selectivity in the zinc-catalysed copolymerisation of CO₂ and cyclohexene oxide

• Sait Elmas,
• Muhammad Afzal Subhani,
• Walter Leitner and
• Thomas E. Müller

Beilstein J. Org. Chem. 2015, 11, 42–49, doi:10.3762/bjoc.11.7

• nucleophilicity of the metal centre [26]. Nevertheless, it is surprising how sharply the selectivity of the CO2/epoxide coupling reaction reverses upon a slight change in the anion. Conclusion In summary, the nature of the anion has a striking effect in the copolymerisation of CO2 and cyclohexene oxide with

A one-pot multistep cyclization yielding thiadiazoloimidazole derivatives

• Debabrata Samanta,
• Anup Rana,
• Jan W. Bats and
• Michael Schmittel

Beilstein J. Org. Chem. 2014, 10, 2989–2996, doi:10.3762/bjoc.10.317

• –π stacking. To take the solvent into consideration, the thermochemical analyses were performed in dichloromethane using the COSMO model with gas phase optimized geometries. Originally, DMAP should be hydrogen bonded to both amide protons in complex 8 increasing the nucleophilicity of both N-centers

Synthesis and biological evaluation of novel N-α-haloacylated homoserine lactones as quorum sensing modulators

• Michail Syrpas,
• Ewout Ruysbergh,
• Christian V. Stevens,
• Norbert De Kimpe and
• Sven Mangelinckx

Beilstein J. Org. Chem. 2014, 10, 2539–2549, doi:10.3762/bjoc.10.265

• lactone carbonyl group, could increase the affinity of AHLs to their cognate receptors [18]. It was shown that introduction of halogens as electron-withdrawing groups in the N-acyl chain reduced the nucleophilicity of the donor oxygen and led to attenuation of the n→π* interaction (Figure 1). Moreover

Regio- and stereoselective synthesis of new diaminocyclopentanols

• Evgeni A. Larin,
• Valeri S. Kochubei and
• Yuri M. Atroshchenko

Beilstein J. Org. Chem. 2014, 10, 2513–2520, doi:10.3762/bjoc.10.262

• planned to evaluate the catalytic efficiency of base promoters such as Cs2CO3 and K2CO3 [39][40][41]. The best result was obtained with Cs2CO3 using DMSO as a solvent (Table 1, entry 11). The catalytic effect of Cs2CO3 could be explained by its ability to increase the poor nucleophilicity of 2-methyl-1H

• nucleophilicity. Moreover, there was not much effect on the outcome of the reactions conducted either under solvent-free conditions or using DMSO as a solvent. The regioisomers 9a–d and 10a–d were isolated through column chromatographic separation and fully characterized in order to avoid ambiguity. The

A versatile δ-aminolevulinic acid (ΑLA)-cyclodextrin bimodal conjugate-prodrug for PDT applications with the help of intracellular chemistry

• Chrysie Aggelidou,
• Theodossis A. Theodossiou,
• Antonio Ricardo Gonçalves,
• Mariza Lampropoulou and
• Konstantina Yannakopoulou

Beilstein J. Org. Chem. 2014, 10, 2414–2420, doi:10.3762/bjoc.10.251

• conditions [(i) ΜeOH, Pd/C, H2, (ii) ΜeOH, formic acid, Pd/C, H2, (iii) ΜeOH, acetic acid, Pd/C, H2, (iv) ΜeOH, trifluoroacetic acid, Pd/C, H2]. A successful alternative was subsequently adopted comprising the linking of 4 to δ-azidolevulinic acid (8) (Scheme 2). The latter, having the nucleophilicity of the

Chiral phosphines in nucleophilic organocatalysis

• Yumei Xiao,
• Zhanhu Sun,
• Hongchao Guo and
• Ohyun Kwon

Beilstein J. Org. Chem. 2014, 10, 2089–2121, doi:10.3762/bjoc.10.218

• elements, thereby providing suitable chirality, nucleophilicity, basicity, functionality, and rigidity. 2 Enantioselective reactions catalyzed by chiral phosphines Using the chiral phosphines described above as catalysts, a number of highly enantioselective reactions have been achieved, offering a wide

Synthesis of a bifunctional cytidine derivative and its conjugation to RNA for in vitro selection of a cytidine deaminase ribozyme

• Nico Rublack and
• Sabine Müller

Beilstein J. Org. Chem. 2014, 10, 1906–1913, doi:10.3762/bjoc.10.198

• . In terms of synthesis efficiency, we first tried to simultaneously deprotect the amino functionality at the nucleobase and the sugar 5'-hydroxy group to generate derivative 12. Thereafter, the greater nucleophilicity of the primary amine over the alcohol should be used for selective amide bond

One-pot stereoselective synthesis of α,β-differentiated diamino esters via the sequence of aminochlorination, aziridination and intermolecular S_N2 reaction

• Yiwen Xiong,
• Ping Qian,
• Chenhui Cao,
• Haibo Mei,
• Jianlin Han,
• Guigen Li and
• Yi Pan

Beilstein J. Org. Chem. 2014, 10, 1802–1807, doi:10.3762/bjoc.10.189

• the relative strong nucleophilicity of benzylamine. Considering the fact that the final product 5a is anti and the aminohalogenation product intermediate A is also anti, the only way to explain the stereochemistry of product 5 is the double inversion via aziridine formation. The direct substitution of