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Letters in Organic Chemistry, Volume 2, No. 4, 2005

 

Contents

 

Advances in 1,3-Dipolar Cycloaddition Reaction of Azides and Alkynes – A Prototype of “Click” Chemistry Pp.293-301

Qian Wang, Srinivas Chittaboina and Hannah N. Barnhill

[Abstract]

 

Letters in Organic Chemistry

 

Effect of Additional Chiral Ligands in Catalytic Enantioselective Addition of Ketene Silyl Acetals to Nitrones Pp.302-305

P. Merino, S. Franco, P. Jimenez, T. Tejero and M.A. Chiacchio

[Abstract]

 

A Novel Route Towards the Synthesis of Stereospecific N-Substituted Chiral Morpholines Pp.306-308

Raid J. Abdel-Jalil, Syed Tasadaque Ali Shah, Khalid Mohammed Khan and Wolfgang Voelter

[Abstract]

 

A Convenient, Highly Selective Iodination Method for Alcohols Using Cesium Iodide/Aluminum Chloride Pp.309-311

Khalid Mohammed Khan, Zia-Ullah, Shahnaz Perveen, M. Iqbal Choudhary, Atta-ur-Rahman and Wolfgang Voelter

[Abstract]

 

A Stereoselective Aldol–Reduction Approach to Polyoxygenated Natural Products. Synthesis of C1–C6 Fragment of Erythronolides Pp.312-315

Marta Galobardes, Miguel Gascon, Pedro Romea and Felix Urpi

[Abstract]

 

Stereoselective Preparation of 1-Deoxy-Homonojirimycin from a b- Ketoester Bearing Sugar Pp.316-318

C. Thomassigny, M.T. Barroso and C. Greck

[Abstract]

 

Highly Stereoselective Alkynylation with Steroidal Alkyne: Efficient Pathway to 24(S) or 24(R)-Hydroxylcholesterol Pp.319-322

Biao Jiang, Zi-li Chen and Hao Huang

[Abstract]  

 

Design of Photo-Reactive Fluorescent Glycosyl Donor for Fabrication of Carbohydrate-Based Functional Materials Pp.323-329

Masaya Suzuki, Yuya Ohguro, Yoshihiro Nishida, Masaki Miyamoto and Kazukiyo Kobayashi

[Abstract]

 

A Simple and Effective Method for the Thionation of Amides to Thioamides Using Al2O3-Supported P4S10 Pp.330-333

Jacques H. Poupaert, Pascal Carato and Christopher R. McCurdy

[Abstract]

 

Microwave and Classical Activation of Solvent-Free Reactions of Nisopropyl Arylidene Amines with Alkyl Cyanoacetates Pp.334-339

Ludovic Paquin, Loic Toupet, Jack Hamelin and Francoise Texier-Boullet

[Abstract]

 

Synthesis of Quinolindione Derivatives Assisted by Microwave Irradiation Pp.340-342

Pietro Campiglia, Teresa Lama, Francesco Aiello, Isabel M. Gomez-Monterrey, Maria V. Diurno, Ettore Novellino and Paolo Grieco

[Abstract]

 

Synthesis of 9-[2-O-(2-Methoxyethyl)-b-D-Ribofuranosyl]purines Using 1-Methanesulfonyloxy-2-Methoxyethane Pp.343-348

Grigorii G. Sivets, Jouko Vepsalainen and Igor A. Mikhailopulo

[Abstract]

 

DNA-Binding Fourfold Spermine Functionalized Perylene Bisimide Dye Pp.349-353

Stefanie Krauß, Marina Lysetska and Frank Wurthner

[Abstract]

 

Natural Phosphate Modified with Sodium Nitrate: New Efficient Catalyst for the Construction of a Carbon-Sulfur and Carbon-Nitrogen Bonds Pp.354-359

Mohamed Zahouily, Hind Charki, Younes Abrouki, Bahija Mounir, Bouchaib Bahlaouan, Ahmed Rayadh and Said Sebti

[Abstract]

 

FeCl3 and FeCl3-SiO2 Catalysed Selective p-Methoxybenzylation of Alcohols with p-Methoxybenzyl Alcohol (PMB-OH) Pp.360-363

Palakodety Radha Krishna, B. Lavanya, A.K. Mahalingam, V.V. Ramana Reddy and G.V.M. Sharma

[Abstract]

 

Formation of Highly Functionalized Hydrindanes and Hydroazulenes via Polyene Cyclization Promoted by the Cross Conjugated a-Carbomethoxy Enone System Pp.364-366

Hsing-Jang Liu, Daqing Sun, Floria Roa-Gutierrez and Kak-Shan Shia

[Abstract]

 

Original Intramolecular SRN1 Reaction in Naphthoquinone Series Pp.367-370

Thierry Terme, Abdelouahab Beziane and Patrice Vanelle

[Abstract]

 

Chloromethoxymethyl Polystyrene (CMM Resin), an Acid Labile Resin for Anchoring/Cleavage of N-Heterocycles and Oxygen Aromatic Compounds Pp.371-373

Marta Marfil, Fernando Albericio and Mercedes Alvarez

[Abstract]

 

A Very Efficient Synthesis of (1H)-1,5-Diazaanthracene-2,9,10-triones Pp.374-377

J. Ignacio Ubeda, Mercedes Villacampa and Carmen Avendano

[Abstract]

 

Synthesis of 6-Amino-1H-Indole-4,7- Quinones Pp.378-381

Eveline Pringel, Jacques Gentili, Raphael Terreux, Bernard Fenet and Roland Barret

[Abstract]

 

Abstracts

 

[Back to top] Advances in 1,3-Dipolar Cycloaddition Reaction of Azides and Alkynes – A Prototype of “Click” Chemistry

Qian Wang, Srinivas Chittaboina and Hannah N. Barnhill

 

Click chemistry, designated by Sharpless and his coworkers, is a modular approach that uses only the most practical and reliable chemical transformations. The Huisgen reaction, especially the newly developed copper(I)-catalyzed 1,2,3-triazole formation reaction between azides and alkynes, is regarded as the “cream of the crop” of click chemistry. In this review, we introduce the recent development of this reaction, and highlight some of its important applications in drug discovery, bioconjugation chemistry, materials development and surface modification.

 

[Back to top] Effect of Additional Chiral Ligands in Catalytic Enantioselective Addition of Ketene Silyl Acetals to Nitrones

P. Merino, S. Franco, P. Jimenez, T. Tejero and M.A. Chiacchio

 

The enantioselectivity of the titanium (IV)-BINOL catalyzed asymmetric Mannich-type reactions of nitrones can be enhanced by using additional chiral ligands. The best results are obtained with diols derived from D-mannitol.

 

[Back to top] A Novel Route Towards the Synthesis of Stereospecific N-Substituted Chiral Morpholines

Raid J. Abdel-Jalil, Syed Tasadaque Ali Shah, Khalid Mohammed Khan and Wolfgang Voelter

 

In this communication a convenient and novel method for the synthesis of chiral N-substituted-(arabinopyrano)[3,4-b]morpholines of pharmacological interest from anhydro sugars is described.

 

[Back to top] A Convenient, Highly Selective Iodination Method for Alcohols Using Cesium Iodide/Aluminum Chloride

Khalid Mohammed Khan, Zia-Ullah, Shahnaz Perveen, M. Iqbal Choudhary, Atta-ur-Rahman and Wolfgang Voelter

 

A variety of allyl and benzyl alcohols are converted into their corresponding iodides using cesium iodide (CsI) in the presence of aluminum chloride (AlCl3) in acetonitrile under mild conditions.

 

[Back to top] A Stereoselective Aldol–Reduction Approach to Polyoxygenated Natural Products. Synthesis of C1–C6 Fragment of Erythronolides

Marta Galobardes, Miguel Gascon, Pedro Romea and Felix Urpi

 

A new synthetic approach directed toward the preparation of C1–C6 fragment of erythronolides is disclosed. The core of the process takes advantage of a highly stereoselective sequence based on a boron– mediated aldol reaction of a lactate–derived chiral ketone followed by a syn-reduction of the resulting adduct.

 

[Back to top] Stereoselective Preparation of 1-Deoxy-Homonojirimycin from a b- Ketoester Bearing Sugar

C. Thomassigny, M.T. Barroso and C. Greck

 

We present in this note the preparation of 1,5,6-trideoxy-1,5-imino-D-gluco-heptitol commonly known as 1-deoxy-homonojirimycin by a diastereoselective way. The polyhydroxylated piperidine has been obtained from a β-ketoester bearing a xylofuranose moiety.

 

[Back to top] Highly Stereoselective Alkynylation with Steroidal Alkyne: Efficient Pathway to 24(S) or 24(R)-Hydroxylcholesterol

Biao Jiang, Zi-li Chen and Hao Huang

 

24(S)- or 24(R)-Hydroxyl cholesterol was prepared in high stereoselectivity (up to 99% de), utilizing asymmetric alkynylation of isobutyraldehyde with steroidal alkyne catalyzed by Zn(OTf)2 respectively in the presence of (1S, 2S)-3-(t-butyldimethylsilyloxyl)-2-N, N-dimethylamino-1-(p-nitrophenyl)- propane-1-ol or its (1R, 2R)-enantiomer.

 

[Back to top] Design of Photo-Reactive Fluorescent Glycosyl Donor for Fabrication of Carbohydrate-Based Functional Materials

Masaya Suzuki, Yuya Ohguro, Yoshihiro Nishida, Masaki Miyamoto and Kazukiyo Kobayashi

 

As a reagent for fabrication of carbohydrate-based functional materials, we prepared a photo-reactive fluorescent glycosyl reagent carrying α-mannoside and 4-azidophenyl group in our previous fluorescent β- peptide skeleton. The reagent increased fluorescence upon UV-irradiation in methanol, demonstrating its high potential utility.

 

[Back to top] A Simple and Effective Method for the Thionation of Amides to Thioamides Using Al2O3-Supported P4S10

Jacques H. Poupaert, Pascal Carato and Christopher R. McCurdy

 

A simple and effective method for the thionation of amides to thioamides using Al2O3-supported P4S10 was developed and applied to a series of amides including some heterocyclic examples. The reaction was best performed in anhydrous dioxane at reflux temperature. Yields ranging from 62 – 93% are comparable to, or superior to those obtained with Lawesson’s reagent. The method uses inexpensive reagents and has the advantage that reagent-derived byproducts may be removed by a simple hydrolytic workup rather than by chromatography, as required for Lawesson’s reagent.

 

[Back to top] Microwave and Classical Activation of Solvent-Free Reactions of Nisopropyl Arylidene Amines with Alkyl Cyanoacetates

Ludovic Paquin, Loic Toupet, Jack Hamelin and Francoise Texier-Boullet

 

Neat imine 1a with alkylcyanoacetate 2 leads to new cyclohexenes by Michael-Michael initiated ring closure reaction at RT or under classical heating. Surprisingly, this cyclohexene is not formed under microwave. This is the first example of a reaction working under classical activation and not under microwaves. A mechanism and an explanation are proposed.

 

[Back to top] Synthesis of Quinolindione Derivatives Assisted by Microwave Irradiation

Pietro Campiglia, Teresa Lama, Francesco Aiello, Isabel M. Gomez-Monterrey, Maria V. Diurno, Ettore Novellino and Paolo Grieco

 

The synthesis of new dihydrothieno[2,3-g and 3,2-g](iso)quinoline-4,9-dione derivatives, as potential templates in development of new cytotoxic agents, was realized using microwave irradiation methodology.

 

[Back to top] Synthesis of 9-[2-O-(2-Methoxyethyl)-b-D-Ribofuranosyl]purines Using 1-Methanesulfonyloxy-2-Methoxyethane

Grigorii G. Sivets, Jouko Vepsalainen and Igor A. Mikhailopulo

 

1-Methanesulfonyloxy-2-methoxyethane (1; MsO-MOE) was used for alkylation of adenosine and 2-aminoadenosine. 2’-O-MOE derivatives of adenosine (3), 2-aminoadenosine (7) and guanosine (10) have been prepared in 47, 44 and 81% isolated yields, respectively. The stereochemistry of the pentofuranose rings of the isomeric 2’-O-MOE and 3’-O-MOE purine nucleosides is very similar and, moreover, alkylation of either 2’- or 3’-hydroxyls has practically no effect upon the stereochemistry of the parent nucleosides.

 

[Back to top] DNA-Binding Fourfold Spermine Functionalized Perylene Bisimide Dye

Stefanie Krauß, Marina Lysetska and Frank Wurthner

 

A spermine functionalized perylene bisimide dye has been synthesized which is highly water soluble at neutral pH and binds effectively to DNA through electrostatic interactions as confirmed by fluorescence and AFM studies.

 

[Back to top] Natural Phosphate Modified with Sodium Nitrate: New Efficient Catalyst for the Construction of a Carbon-Sulfur and Carbon-Nitrogen Bonds

Mohamed Zahouily, Hind Charki, Younes Abrouki, Bahija Mounir, Bouchaib Bahlaouan, Ahmed Rayadh and Said Sebti

 

The modification on natural phosphate (NP) with sodium nitrate by calcination catalyzed Michael addition of mercaptans and amines to chalcone derivatives with high yields under mild reaction conditions. By-products of usual undesirable reaction in Michael condensation such as 1,2-addition, bis-addition and polymerization are not observed. The work-up procedure is simplified by simple filtration with the use of Na/NP-2. This catalyst is used for the facile synthesis of b-amino acid and b-amino diacid under heterogeneous conditions.

 

[Back to top] FeCl3 and FeCl3-SiO2 Catalysed Selective p-Methoxybenzylation of Alcohols with p-Methoxybenzyl Alcohol (PMB-OH)

Palakodety Radha Krishna, B. Lavanya, A.K. Mahalingam, V.V. Ramana Reddy and G.V.M. Sharma

 

Anhydrous FeCl3 and FeCl3-SiO2 serve as Lewis acids for direct conversion of alcohols into p-methoxybezyl ethers using PMB-OH in good yields, the latter reagent was found to be effective in not only converting primary, allylic and propargylic alcohols selectively but also the pre-existing acid sensitive groups remained unscathed.

 

[Back to top] Formation of Highly Functionalized Hydrindanes and Hydroazulenes via Polyene Cyclization Promoted by the Cross Conjugated a-Carbomethoxy Enone System

Hsing-Jang Liu, Daqing Sun, Floria Roa-Gutierrez and Kak-Shan Shia

 

The polyene cyclization promoted by the cross conjugated a-carbomethoxy enone system has been successfully applied to facilitate the construction of the hydridane and hydroazulene framework containing a high level of functionalization.

 

[Back to top] Original Intramolecular SRN1 Reaction in Naphthoquinone Series

Thierry Terme, Abdelouahab Beziane and Patrice Vanelle

 

We report here the synthesis of a new cyclopenta[b]naphthalene-4,7-dione via the first example of intramolecular electron transfer reaction from naphthoquinonic alkylating agent bearing a nitroalkane group at the position 3.

 

[Back to top] Chloromethoxymethyl Polystyrene (CMM Resin), an Acid Labile Resin for Anchoring/Cleavage of N-Heterocycles and Oxygen Aromatic Compounds

Marta Marfil, Fernando Albericio and Mercedes Alvarez

 

A novel linker for the solid-phase anchoring of heterocycles and phenol compounds is described.

 

[Back to top] A Very Efficient Synthesis of (1H)-1,5-Diazaanthracene-2,9,10-triones

J. Ignacio Ubeda, Mercedes Villacampa and Carmen Avendano

 

Acylation of ortho-lithiated species derived from N,O-dipivaloyl-6-amino-5,8-dimethoxy-4-methyl- 2(1H)-quinolinone, followed by condensation with carbonyl reagents and in situ N-deprotection gave 7-alkyl or 6,7-dialkyl-9,10-dimethoxy-4-methyl-1,5-diaza-2(1H)-anthracenones, which were finally oxidised to the title compounds.

 

[Back to top] Synthesis of 6-Amino-1H-Indole-4,7- Quinones

Eveline Pringel, Jacques Gentili, Raphael Terreux, Bernard Fenet and Roland Barret

 

The addition of amines to N-benzenesulfonylindoloquinone and the regiochemistry of the products are studied.