Nitroso Diels-Alder Reaction Research Articles

ChemInform Abstract: Nitroso Diels—Alder (NDA) Reaction as an Efficient Tool for the Functionalization of Diene‐Containing Natural Products

AbstractReview: [170 refs.

Nitroso Diels-Alder (NDA) reaction as an efficient tool for the functionalization of diene-containing natural products.

This review describes the use of nitroso Diels-Alder reactions for the functionalization of complex diene-containing natural products in order to generate libraries of compounds with potential biological activity. The application of this methodology to the structural modification of a series of natural products (thebaine, steroidal dienes, rapamycin, leucomycin, colchicine, isocolchicine and piperine) is discussed using relevant examples from the literature from 1973 onwards. The biological activity of the resulting compounds is also discussed. Additional comments are provided that evaluate the methodology as a useful tool in organic, bioorganic and medicinal chemistry.

New and Concise Syntheses of the Bicyclic Oxamazin Core Using an Intramolecular Nitroso Diels–Alder Reaction and Ring-Closing Olefin Metathesis

Herein two new and concise synthetic approaches for making an unsaturated bicyclic oxamazin core are reported. The first involves the use of an intramolecular Diels-Alder reaction to form both of the fused rings in one step. The second approach incorporates ring-closing olefin metathesis in the final step to form the second fused ring of the core. The scope of the second approach was also expanded further to afford larger ringed bicyclic systems.

Regio- and Diastereoselective Nitroso Diels-Alder Cycloaddition Reactions of 3-dienyl-2-azetidinones with Nitrosoarenes

The regioselective nitroso Diels-Alder (NDA) reactions of trans 3-butadienyl-2-azetidinones with nitrosoarenes leading to the synthesis of novel and diastereomerically pure 3-(3,6-dihydro-2H-1, 2-oxazin-6-yl) azetidin-2-one derivatives and cis 3-butadienyl-2-azetidinones resulting in a diastereoselective mixture of regioisomers are investigated. The observed regioselective behavior is supported by computational model, Ab initio [HF/6-31G (d)] and density functional theory [B3LYP/6-31G (d)] calculations. Additionally, the effect of solvation (in dichloromethane) in these reactions was also investigated in order to mimic the experimental solvent conditions. Keywords: 1, 2-oxazinyl-azetidine-2-one, 3-Dienyl-β-lactams, DFT calculations, nitroso diels-Alder reactions, nitrosoarenes, streptazolin, lepadins, 6-epitrehazolin, lyxopiperidinose, lycoricidine

Synthesis of all-cis 2,5-imino-2,5-dideoxy-fucitol and its evaluation as a potent fucosidase and galactosidase inhibitor

We here describe a simple and efficient synthetic method for a non-hydrolysable precursor of a GDP-fucose analogue: The synthesis of the racemic aminofuranofucitol 3 from sorbic alcohol by nitroso-Diels-Alder reaction. This 'all-cis-pyrrolidine', with all substituents occupying a cis position, has been determined as a potent inhibitor of α-L-fucosidase and a moderate inhibitor of α- and β-D-galactosidase. The good recognition of this fucose moiety analogue by specific enzymes is thus confirmed. The C-anomeric bond in this particular structure is in the β-position and makes this compound an interesting candidate for further chemical modifications. Influence of the methyl and hydroxymethyl groups on the inhibition potency is discussed.

ChemInform Abstract: Syntheses and Antibacterial Activity Studies of New Oxazolidinones from Nitroso Diels—Alder Chemistry.

AbstractA series of novel oxazolidinone antibiotics, e.g. (III) and (V), having [2.2.1] and [2.2.2] bicyclic oxazine moieties at the C‐5 side chain of the A‐ring is synthesized via nitroso Diels—Alder reaction.

New chiral amino acid-derived α-acyloxynitroso reagents for asymmetric nitroso Diels–Alder reactions

The preparation of new chiral α-acyloxynitroso derivatives 4a– e as chiral dienophiles for the nitroso Diels–Alder reaction is reported. These compounds are obtained from amino acid-derived iodobenzene dicarboxylates and ketoximes, and are stable and easy-to-handle reagents. Initial studies for their nitroso Diels–Alder reactions with cyclohexadiene are also reported.

Corrigendum to “Syntheses of structurally diverse amino acids, including δ-hydroxylysine, using the acyl nitroso Diels–Alder reaction” [Tetrahedron Lett. 51 (2010) 2160

Corrigendum to “Syntheses of structurally diverse amino acids, including δ-hydroxylysine, using the acyl nitroso Diels–Alder reaction” [Tetrahedron Lett. 51 (2010) 2160

Syntheses of structurally diverse amino acids, including δ-hydroxylysine, using the acyl nitroso Diels–Alder reaction

Abstract By virtue of its ability to introduce amino and hydroxy functionalities in a 1,4-relationship with fully controlled relative stereochemistry, the acyl nitroso Diels–Alder (ANDA) reaction is ideally suited to the synthesis of structurally diverse, including hydroxylated, amino acids. The major issue to be tackled is that of regiochemistry in the ANDA addition to unsymmetrical dienes. The transformation of three diverse types of ANDA adducts into amino acids is described, in particular, the synthesis of δ-hydroxylysine, an important constituent of collagen, as a single (2SR, 5SR) diastereoisomer in protected form.

Preparation and biological evaluation of novel leucomycin analogs derived from nitroso Diels–Alder reactions

A series of 10,13-disubstituted 16-membered macrolides was synthesized using nitroso Diels-Alder reactions of leucomycin A7. Despite the extensive constituent functionalities in leucomycin, the hetero cycloaddition reactions proceeded in a highly regio- and stereoselective fashion. Subsequent chemical modifications of the nitroso cycloadducts, including N-O bond reduction, were also conducted. Most leucomycin derivatives retained antibiotic profiles similar to leucomycin A7, and, in contrast to leucomycin itself, several exhibited moderate antiproliferative and cytotoxic activity.

Syntheses and antibacterial activity studies of new oxazolidinones from nitroso Diels–Alder chemistry

A series of novel oxazolidinone antibiotics having [2.2.1] and [2.2.2] bicyclic oxazine moieties at the C-5 side chain of the A-ring was synthesized by nitroso Diels–Alder reactions, from three linezolid analogs containing morpholine, piperazine and thiomorpholine, respectively, as the C-ring components. Subsequent N–O bond cleavage generated oxazolidinones with 4-amino cyclo-2-en-1-ol substituents. The in vitro antibacterial activities of these oxazolidinone analogs were evaluated.

Syntheses and biological activity studies of novel sterol analogs from nitroso Diels-Alder reactions of ergosterol.

A series of novel sterol analogs was prepared using nitroso Diels-Alder reactions with ergosterol. Most cycloaddition reactions proceeded in an excellent regio- and stereoselective fashion. Further N-O bond cleavage of cycloadducts generated compounds with biological activity in PC-3 and MCF-7 cancer cell lines.

ChemInform Abstract: Total Synthesis of (+)‐trans‐Dihydronarciclasine by a Catalytic Enantioselective Regiodivergent Nitroso Diels—Alder Reaction.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Total Synthesis of (+)‐trans‐Dihydronarciclasine by a Catalytic Enantioselective Regiodivergent Nitroso Diels–Alder Reaction

A novel approach to enantiomerically pure (+)-trans-dihydronarciclasine (1), a biologically active natural product of the Amaryllidaceae group, uses a catalytic enantioselective regiodivergent nitroso Diels–Alder reaction as the key step. Compound 1 is prepared in a 17-step synthesis in 5.6 % overall yield. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2111/2008/z800903_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Divergent Reactions for Racemates: Catalytic, Enantioselective, and Regiodivergent Nitroso Diels–Alder Reactions

Divergent Reactions for Racemates: Catalytic, Enantioselective, and Regiodivergent Nitroso Diels–Alder Reactions

Recent Advances in Asymmetric Nitroso Diels—Alder Reactions

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Recent Advances in Asymmetric Nitroso Diels–Alder Reactions

AbstractDuring the past decade, the nitroso Diels–Alder (NDA) reaction has become more practical tool for organic synthesis, and a numbers of important compounds have been synthesized using this method. Until recently, no reports on a catalytic asymmetric version of this reaction had been reported; the major issues were the high reactivity of nitroso compounds and their chemical properties. This microreview outlines recent advances in the area of asymmetric NDA reaction following the review by Streith and Defoin in 1994. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Rich Chemistry of Nitroso Compounds

AbstractFor Abstract see ChemInform Abstract in Full Text.

Rich chemistry of nitroso compounds

Nitrosobenzene or nitrosopyridine are found to be attractive electrophiles in catalytic enantioselective carbon-nitrogen and/or carbon-oxygen bond forming reactions. In the presence of designer Lewis or Brønsted acid catalysts, catalytic enantioselective O- and N-nitroso aldol reaction or nitroso Diels-Alder reaction proceed smoothly. The scope and limitation of new catalytic processes are described.

Catalytic, Highly Enantio‐, and Diastereoselective Nitroso Diels—Alder Reaction.

AbstractFor Abstract see ChemInform Abstract in Full Text.