Synthesis of hapten-phosphoramidites from 2′-deoxyuridine

A total of 11 novel phosphoramidites, 3a-d, 4a-d and 14a-c were prepared from 2′-deoxyuridine functionalized at 5 and 6-position of the pyrimidine ring with hapten reporter groups, e.g. adamantane, carbazole, dansyl and dabsyl, suitable for use in immunodetection nucleic acid testing assays.     

Synthesis of oligo-2′-<Emphasis Type="Italic">O</Emphasis>-methylribonucleotides containing α-amino acid residues in 2′-position

Oligo-2′-O-methylribonucleotides containing residues of phenylalanine, histidine, and lysine amides were synthesized with the use of new phosphoramidites of 2′-aminoacid derivatives of uridine. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 775–783, April, 2007.     

Ni‐Catalyzed Asymmetric Cycloisomerization of Dienes by Using TADDOL Phosphoramidites

A library of α,α,α,α‐tetraaryl‐1,3‐dioxolane‐4,5‐dimethanol (TADDOL)‐based phosphoramidites has been synthesized and applied in the Ni‐catalyzed cycloisomerization of different dienes. Through the systematic variation of the three structural motifs of the lead structure, that is, the amine moiety, the protecting group, and the aryl substituents, the ligand features could be optimized for the asymmetric cycloisomerization of the model substrate diethyl diallylmalonate. The substrate scope of the new catalytic system was extended to other diallylic substrates, including unsymmetrical dienes. Overall remarkably high activities of up to approximately 13 500 h^?1, very high selectivities toward five‐membered exo‐methylenecyclopentanes, and enantioselectivities of up to 92 % ee have been achieved.     

Unravelling the reaction path of rhodium-MonoPhos-catalysed olefin hydrogenation

The mechanism of the asymmetric hydrogenation of methyl (Z)-2-acetamidocinnamate (mac) catalysed by [Rh(MonoPhos)(2)(nbd)]SbF(6) (MonoPhos: 3,5-dioxa-4-phosphacyclohepta[2,1-a:3,4-a']dinaphthalen-4-yl)dimethylamine) was elucidated by using (1)H, (31)P and (103)Rh NMR spectroscopy and ESI-MS. The use of nbd allows one to obtain in pure form the rhodium complex that contains two units of the ligand. In contrast to the analogous complexes that contain cis,cis-1,5-cyclooctadiene (cod), this complex shows well-resolved NMR spectroscopic signals. Hydrogenation of these catalyst precursors at 1 bar total pressure gave rise to the formation of a bimetallic complex of general formula [Rh(MonoPhos)(2)](2)(SbF(6))(2); no solvate complexes were detected. In the dimeric complex both rhodium atoms are ligated to two MonoPhos ligands but, in addition, each rhodium atom also binds to one of the binaphthyl rings of a ligand that is bound to the other rhodium metal. Upon addition of mac, a mixture of diastereomeric complexes [Rh(MonoPhos)(2)(mac)]SbF(6) is formed in which the substrate is bound in a chelate fashion to the metal. Upon hydrogenation, these adducts are converted into a new complex [Rh(MonoPhos)(2){mac(H)(2)}]SbF(6) in which the methyl phenylalaninate mac(H)(2) is bound through its aromatic ring to rhodium. Addition of mac to this complex leads to displacement of the product by the substrate. No hydride intermediates could be detected and no evidence was found for the involvement at any stage of the process of complexes with only one coordinated MonoPhos. The collected data suggest that the asymmetric hydrogenation follows a Halpern-like mechanism in which the less abundant substrate-catalyst adduct is preferentially hydrogenated to phenylalanine methyl ester.     

Synthesis of the First Tellurium‐Derivatized Oligonucleotides for Structural and Functional Studies

We report here the first synthesis of Te‐nucleoside phosphoramidites and Te‐modified oligonucleotides. We protected the 2′‐tellurium functionality by alkylation and found that the Te functionality is compatible with solid‐phase synthesis and that the Te oligonucleotides are stable during deprotection and purification. In addition, the redox properties of the Te functionalities have been explored. We found that the telluride and telluoxide DNAs are interchangeable by redox reactions. At elevated temperature, the Te‐DNA can also be site‐specifically fragmented oxidatively or reductively when 2′‐TePh functionality is present, whereas elimination of the nucleobase is observed in the presence of 2′‐TeMe. Moreover, the stability of the DNA duplexes derivatized with the Te functionalities has been investigated. Our Te derivatization of nucleic acids provides a novel approach for investigating DNA damage as well as for structure and function studies of nucleic acids and their protein complexes.     

Iridium‐Catalyzed Allylic Substitutions with Cyclometalated Phosphoramidite Complexes Bearing a Dibenzocyclooctatetraene Ligand: Preparation of (π‐Allyl)Ir Complexes and Computational and NMR Spectroscopic Studies

(π‐Allyl)Ir complexes derived from dibenzocyclooctatetraene and phosphoramidites by cyclometalation are effective catalysts for allylic substitution reactions of linear monosubstituted allylic carbonates. These catalysts provide exceptionally high degrees of regioselectivity and allow the reactions to be run under aerobic conditions. A series of (π‐allyl)Ir complexes were prepared and characterized by X‐ray crystal structure analyses. An allylic amination with aniline displayed different resting states depending on the presence of a strong base. DFT calculations were carried out on the mechanistic aspects of these reactions. The results suggest that for the (π‐allyl)Ir complexes, the formation and reactions with nucleophiles proceed with comparable rates.     

New oxazoline-containing phosphoramidite ligand for palladium-catalyzed asymmetric allylic sulfonylation

New chiral oxazoline-containing phosphoramidite was synthesized and its complex formation with rhodium(i) and palladium(ii) was examined. The new ligand is a highly efficient chiral inductor (ee up to 92%) in palladium-catalyzed asymmetric sulfonylation of 1,3-diphenylallyl acetate with sodium p-toluenesulfinate.