Oligonucleotide Analogues with Integrated Bases and Backbone. Part 15 : Synthesis and Association of Ethenylene-Linked Self-Complementary Dimers
✍ Scribed by Xiaomin Zhang; Bruno Bernet; Andrea Vasella
- Publisher
- John Wiley and Sons
- Year
- 2007
- Tongue
- German
- Weight
- 510 KB
- Volume
- 90
- Category
- Article
- ISSN
- 0018-019X
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✦ Synopsis
The self-complementary (Z)-configured U*[c e ]A ( * ) dinucleotide analogues 6, 8, 10, 12, 14, and 16, and the A*[c e ]U ( * ) dimers 19, 21, 23, 25, 27, and 29 were prepared by partial hydrogenation of the corresponding ethynylene linked dimers. Photolysis of 14 led to the (E)-alkene 17. These dinucleotide analogues associate in CDCl 3 solution, as evidenced by NMR and CD spectroscopy. The thermodynamic parameters of the duplexation were determined by vant Hoff analysis. The (Z)-configured U*[c e ]A ( * ) dimers 14 and 16 form cyclic duplexes connected by Watson -Crick H-bonds, the (E)-configured U*[c e ]A dimer 17 forms linear duplexes, and the U*[c e ]A ( * ) allyl alcohols 6, 8, 10, and 12 form mixtures of linear and cyclic duplexes. The C(6/I)-unsubstituted A*[c e ]U allyl alcohols 19 and 23 form linear duplexes, whereas the C(6/I)-substituted A*[c e ]U* allyl alcohols 21 and 25, and the C(5'/I)-deoxy A*[c e ]U ( * ) dimers 27 and 29 also form minor amounts of cyclic duplexes. The influence of intra-and intermolecular H-bonding of the allyl alcohols and the influence of the base sequence upon the formation of cyclic duplexes are discussed.
📜 SIMILAR VOLUMES
The self-complementary, ethylene-linked U\*[c a ]A ( \* ) dinucleotide analogues 8, 10, 12, 14, 16, and 18, and the sequence-isomeric A\*[c a ]U ( \* ) analogues 20, 22, 24, 26, 28, and 30 were obtained by Pd/Ccatalyzed hydrogenation of the corresponding, known ethynylene-linked dimers. The associat
## Abstract The self‐complementary tetrameric propargyl triols **8, 14, 18**, and **21** were synthesized to investigate the duplex formation of self‐complementary, ethynylene‐linked UUAA, AAUU, UAUA, and AUAU analogues with integrated bases and backbone (ONIBs). The linear synthesis is based on re
## Abstract The thiomethylene‐linked U\*[s]U^(^\*^)^ dimers **9**–**14** were synthesized by substitution of the 6‐[(mesyloxy)methyl]uridine **6** by the thiolate derived from the uridine‐5′‐thioacetates **7** and **8** followed by __O__‐deprotection. Similarly, the thiomethylene‐linked A\*[s]A^(^\