Gold(I)-catalysed one-pot synthesis of chromans using allylic alcohols and phenols

• Eloi Coutant,
• Paul C. Young,
• Graeme Barker and
• Ai-Lan Lee

Beilstein J. Org. Chem. 2013, 9, 1797–1806, doi:10.3762/bjoc.9.209

• , entries 8–10). Firstly, no reaction is observed in the absence of a catalyst (Table 1, entry 8). The Brønsted acid catalyst HNTf2 does form chroman 8, but in a poorer isolated yield (21%, Table 1, entry 9) and the silver salt [76] AgNTf2 as a catalyst does not provide any 8, yielding only 9 and 10 (Table

Gallium-containing polymer brush film as efficient supported Lewis acid catalyst in a glass microreactor

• Rajesh Munirathinam,
• Roberto Ricciardi,
• Richard J. M. Egberink,
• Jurriaan Huskens,
• Michael Holtkamp,
• Herbert Wormeester,
• Uwe Karst and
• Willem Verboom

Beilstein J. Org. Chem. 2013, 9, 1698–1704, doi:10.3762/bjoc.9.194

• Polystyrene sulfonate polymer brushes, grown on the interior of the microchannels in a microreactor, have been used for the anchoring of gallium as a Lewis acid catalyst. Initially, gallium-containing polymer brushes were grown on a flat silicon oxide surface and were characterized by FTIR, ellipsometry, and

• walls using polymer brushes. As a part of this program, herein, we report the anchoring of gallium as a Lewis acid catalyst making use of polystyrene sulfonate (PSS) polymer brushes. The choice for gallium was inspired by the successful application of solid supported gallium triflate to catalyze the

• the best of our knowledge, we described the first example of the application of polystyrene sulfonate-based polymer brushes to anchor gallium as a Lewis acid catalyst onto the microchannel interior of a microreactor and proved its catalytic activity for the dehydration of oximes to the corresponding

An aniline dication-like transition state in the Bamberger rearrangement

• Shinichi Yamabe,
• Guixiang Zeng,
• Wei Guan and
• Shigeyoshi Sakaki

Beilstein J. Org. Chem. 2013, 9, 1073–1082, doi:10.3762/bjoc.9.119

• water from Ar–N+H2OH is rate determining and a diprotonated species, Ar–N+H2OH2+, contributes significantly to the observed reaction rate at the acid-catalyst concentration [H2SO4] > 0.50 mol/L. The activation energy of the rearrangement in Scheme 1 was measured to be 24.8 kcal/mol. The SN1 mechanism

Synthesis of meso-substituted dihydro-1,3-oxazinoporphyrins

• Satyasheel Sharma and
• Mahendra Nath

Beilstein J. Org. Chem. 2013, 9, 496–502, doi:10.3762/bjoc.9.53

• -triphenylporphyrin using SnCl2 under acidic conditions [41][42]. Firstly, meso-(4-aminophenyl)porphyrin 1 was reacted with salicylaldehyde or 5-chlorosalicylaldehyde in the presence of La(OTf)3 as a Lewis acid catalyst in toluene under reflux to afford the corresponding iminoporphyrins 2 and 3, which on reduction by

The Amadori rearrangement as glycoconjugation method: Synthesis of non-natural C-glycosyl type glycoconjugates

• Katharina Gallas,
• Gerit Pototschnig,
• Florian Adanitsch,
• Arnold E. Stütz and
• Tanja M. Wrodnigg

Beilstein J. Org. Chem. 2012, 8, 1619–1629, doi:10.3762/bjoc.8.185

• 1 and a suitable amine under acid catalysis (Scheme 1). The reaction is known to be very sensitive to the nature of the carbohydrate substrate, the acid catalyst, and the amino component, as well as to the temperature and duration. Additionally, some challenges accompany the reaction limiting its

Discovery of practical production processes for arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides): Beginning of a new era of “super-trifluoromethyl” arene chemistry and its industry

• Teruo Umemoto,
• Lloyd M. Garrick and
• Norimichi Saito

Beilstein J. Org. Chem. 2012, 8, 461–471, doi:10.3762/bjoc.8.53

• to be thermal isomerization of trans-2a to cis-2a with an acid catalyst, suggesting that the cis-isomer is more thermodynamically stable than the trans-isomer. With ZnF2/SbCl5 the cis-isomer was barely detected (run 11, Table 3). The ratio of trans-2a:cis-2a:PhSF5 was 385:0:100 after 10 min; 63:trace

Efficient, highly diastereoselective MS 4 Å-promoted one-pot, three-component synthesis of 2,6-disubstituted-4-tosyloxytetrahydropyrans via Prins cyclization

• Naseem Ahmed and
• Naveen Kumar Konduru

Beilstein J. Org. Chem. 2012, 8, 177–185, doi:10.3762/bjoc.8.19

• -tosyloxytetrahydropyrans was performed. The synthesis features an optimized Prins cyclization in which an aromatic homoallylic alcohol, an aromatic/aliphatic aldehyde, and p-toluenesulfonic acid (catalyst and reagent) are reacted in the presence of molecular sieves (MS) 4 Å at reflux in dichloromethane to afford excellent

• and unsymmetrical tetrahydropyrans can be synthesized. p-Toluenesulfonic acid (PTSA) is reported as a versatile Brønsted acid catalyst in various organic transformations [32][33][34]. Previously, PTSA has been used as a catalyst in Prins cyclizations but the product yields were low even under extended

• conclusion, we have reported a simple and efficient one-pot three-component synthesis of highly diastereoselective and functionalized 2,6-disubstituted-4-tosyloxytetrahydropyrans via Prins cyclization. An aromatic homoallylic alcohol, an aromatic/aliphatic aldehyde, and p-toluenesulfonic acid (catalyst and

Continuous-flow hydration–condensation reaction: Synthesis of α,β-unsaturated ketones from alkynes and aldehydes by using a heterogeneous solid acid catalyst

• Magnus Rueping,
• Teerawut Bootwicha,
• Hannah Baars and
• Erli Sugiono

Beilstein J. Org. Chem. 2011, 7, 1680–1687, doi:10.3762/bjoc.7.198

• employing a heterogeneous solid acid catalyst [66][67][68][69][70][71][72][73][74][75][76][77][78][79][80][81][82][83][84]. The continuous-flow apparatus for the experiment was set up according to Scheme 1. A 10 mL reaction vessel was charged with the heterogeneous solid acid catalyst (10 g) and inserted

• . Our initial reaction development was focussed on finding the optimal conditions for the continuous-flow reaction of phenylacetylene (1a) with benzaldehyde (2a) applying the ion-exchange resin amberlyst-15 [85] as heterogeneous solid acid catalyst. The effects of the substrate concentration, the

• mixture of alkyne 1 and aldehyde 2 was constantly pumped into the flow cell, filled with the solid acid catalyst and solvent, at the flow rate of 0.5 mL min−1 under microwave irradiation. This was followed by a washing procedure with 100 mL of solvent and then the next substrate was introduced

Efficient and selective chemical transformations under flow conditions: The combination of supported catalysts and supercritical fluids

• M. Isabel Burguete,
• Eduardo García-Verdugo and
• Santiago V. Luis

Beilstein J. Org. Chem. 2011, 7, 1347–1359, doi:10.3762/bjoc.7.159

• bis-substituted ones [71]. The use of an acid catalyst (Amberlyst 15) allows the formation of the corresponding mono-ethers by reaction of 1,6-hexanediol and other diols with simple alcohols under flow conditions (scCO2, 150 °C, 20 MPa, 1.15 mL·min−1). One of the most interesting results found was the

• combination of a supported enzyme (Novozym 435) and a supported acid catalyst, both covered by a thin layer of an IL. This has allowed the development of the continuous chemoenzymatic dynamic kinetic resolution of the corresponding racemic alcohols with yields of up to 80% and enantioselectivities of about 91

• mixture of zeolite CP811E-150 as the acid catalyst for the racemization and CALB supported on a SILLP based on bead-type PS-DVB resins [106]. Good results were obtained when the zeolite catalyst was coated with a small amount of an IL. This follows the same trend observed in the case of SILPs

Convergent synthesis of the tetrasaccharide repeating unit of the O-antigen of Shigella boydii type 9

• Abhishek Santra and
• Anup Kumar Misra

Beilstein J. Org. Chem. 2011, 7, 1182–1188, doi:10.3762/bjoc.7.137

• reduced the number of protection–deprotection steps. A number of modified clean reaction methodologies have been applied for the preparation of intermediates. HClO4–SiO2 has been used as an effective acid catalyst to activate glycosyl trichloroacetimidate derivative and thioglycoside in combination with

SbCl₃-catalyzed one-pot synthesis of 4,4′-diaminotriarylmethanes under solvent-free conditions: Synthesis, characterization, and DFT studies

• Ghasem Rezanejade Bardajee

Beilstein J. Org. Chem. 2011, 7, 135–144, doi:10.3762/bjoc.7.19

• the reaction can be summarized as a tandem regioselective electrophilic aromatic substitution reaction of N,N-dimethylaniline and aldehydes, in which SbCl3 (as a Lewis acid catalyst) activates the carbonyl group of the aldehydes. If we accept this mechanism, one can expect a general influence of

Kinetics and mechanism of vanadium catalysed asymmetric cyanohydrin synthesis in propylene carbonate

• Michael North and
• Marta Omedes-Pujol

Beilstein J. Org. Chem. 2010, 6, 1043–1055, doi:10.3762/bjoc.6.119

• established that the asymmetric addition of TMSCN to aldehydes can be catalysed by both Lewis acids and Lewis bases [1]. A Lewis acid catalyst activates the aldehyde by formation of an aldehyde-Lewis acid complex (e.g., 4) whilst a Lewis base catalyst activates the TMSCN through formation of a hypervalent

• position of the aldehyde during the transition state, and hence that complex 1 functioned predominantly as a Lewis acid catalyst, activating the aldehyde towards attack by cyanide, and resulting in more charge transfer to the benzylic position of the aldehyde during the transition state for formation of

A review of new developments in the Friedel–Crafts alkylation – From green chemistry to asymmetric catalysis

• Magnus Rueping and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2010, 6, No. 6, doi:10.3762/bjoc.6.6

• environmentally and economically benign processes, the development of FC reactions using only catalytic amounts of a metal or acid catalyst would be highly desirable. In addition, the substitution of the alkyl chlorides by other, less toxic, alkylating reagents such as alcohols would be a major improvement as

• –Crafts conditions using stoichiometric amounts of a Lewis acid, such as AlCl3. With the need for more environmentally and economically benign processes, the Friedel–Crafts-type synthesis of 1,1-diarylalkanes using catalytic amounts of a metal or acid catalyst and more environmental friendly benzylation

• mol% Mo(CO)6 as the Lewis acid catalyst under the strict exclusion of air and moisture, the Fukuzawa group utilized Sc(OTf)3 as a water and air tolerant catalyst. Various arenes, including benzene, p-xylene, or mesitylenes were alkylated with benzyl alcohols 4 to afford the desired 1,1-diarylalkanes 5

DBFOX- Ph/metal complexes: Evaluation as catalysts for enantioselective fluorination of 3-(2-arylacetyl)-2-thiazolidinones

• Takehisa Ishimaru,
• Norio Shibata,
• Dhande Sudhakar Reddy,
• Takao Horikawa,
• Shuichi Nakamura and
• Takeshi Toru

Beilstein J. Org. Chem. 2008, 4, No. 16, doi:10.3762/bjoc.4.16

• with moderate to good enantioselectivities (up to 78% ee) when the reaction was carried out in the presence of DBFOX-Ph (11 mol%), Ni(ClO4)2·6H2O (10 mol%) and 2,6-lutidine (0 or 1.0 equiv) in CH2Cl2. Keywords: fluorination; enantioselective; nickel; Lewis acid; catalyst; Background Enantioselective

The first organocatalytic carbonyl- ene reaction: isomerisation- free C-C bond formations catalysed by H-bonding thio- ureas

• Matthew L. Clarke,
• Charlotte E. S. Jones and
• Marcia B. France

Beilstein J. Org. Chem. 2007, 3, No. 24, doi:10.1186/1860-5397-3-24

• Lewis acid catalyst. [1][2][3][4] One of the drawbacks of the intermolecular carbonyl ene reaction is substrate scope. The majority of all successful catalytic ene reactions have utilised the highly activated glyoxylate esters as enophile. Extending asymmetric intramolecular carbonyl ene reactions to

Asymmetric aza-Diels- Alder reaction of Danishefsky's diene with imines in a chiral reaction medium

• Bruce Pégot,
• Olivier Nguyen Van Buu,
• Didier Gori and
• Giang Vo-Thanh

Beilstein J. Org. Chem. 2006, 2, No. 18, doi:10.1186/1860-5397-2-18

• Danishefsky's diene in chiral ionic liquids provides the corresponding cycloadduct with moderate to high diastereoselectivity. The reaction has proved to perform better at room temperature in ionic liquids without either Lewis acid catalyst or organic solvent. Chiral ionic liquids are recycled while their

• highly efficient procedure for the synthesis of 2-substituted-2,3-dihydro-4-pyridone derivatives through the aza-Diels-Alder reaction under 'green chemistry' conditions. The reaction has been found to perform well at room temperature in ionic liquids using no Lewis acid catalyst or organic solvent.[30

• solvent-free microwave activation. All aza-Diels-Alder reactions were performed under argon at room temperature without either a Lewis acid catalyst or organic solvent (Table 1). As illustrated in Table 1, both yield and diastereoselectivity are highest when performing the experiment with 2 equivalents of

Study of thioglycosylation in ionic liquids

• Jianguo Zhang and
• Arthur Ragauskas

Beilstein J. Org. Chem. 2006, 2, No. 12, doi:10.1186/1860-5397-2-12

• . reported that the glycosidations of glucopyranosyl fluorides with assorted alcohols employing an ionic liquid and a protic acid catalyst proceeded, under mild conditions, to afford the corresponding glycosides in 54–91% yields.[7] The stereoselectivity of the glycosidation was significantly affected by the

An efficient synthesis of novel pyrano[2,3-d]- and furopyrano[2,3-d]pyrimidines via indium- catalyzed multi- component domino reaction

• Dipak Prajapati and
• Mukut Gohain

Beilstein J. Org. Chem. 2006, 2, No. 11, doi:10.1186/1860-5397-2-11

• Mukaiyama Aldol reactions, Friedel-Crafts acylations,[6] Pavarob reactions[7] and Diels-Alder reactions[8] in water. Since the work of Loh,[8] indium halide has also been shown to be an effective Lewis acid catalyst for various reactions in aqueous media. [9][10] However, its use in the hetero Diels-Alder

High stereoselectivity on low temperature Diels- Alder reactions

• Luiz Carlos da Silva Filho,
• Valdemar Lacerda Júnior,
• Mauricio Gomes Constantino,
• Gil Valdo José da Silva and
• Paulo Roberto Invernize

Beilstein J. Org. Chem. 2005, 1, No. 14, doi:10.1186/1860-5397-1-14

• , Brazil 10.1186/1860-5397-1-14 Abstract We have found that some of the usually poor dienophiles (2-cycloenones) can undergo Diels-Alder reaction at -78°C with unusually high stereoselectivity in the presence of niobium pentachloride as a Lewis acid catalyst. A remarkable difference in reaction rates for

Synthesis and glycosidase inhibitory activity of new hexa- substituted C8-glycomimetics

• Olivia Andriuzzi,
• Christine Gravier-Pelletier,
• Gildas Bertho,
• Thierry Prangé and
• Yves Le Merrer

Beilstein J. Org. Chem. 2005, 1, No. 12, doi:10.1186/1860-5397-1-12

• acid catalyst such as ytterbium triflate, revealed unsuccessful, only leading to recover the starting material. To overcome this difficulty, we turned to a more electrophilic sulfate moiety [36] (Scheme 3). Thus, treatment of the cis-diols 3 and 4 with thionyl chloride in the presence of triethylamine