title: Syntheses of heterocyclic ethenyl C-nucleosides for recognition of inverted base pairs within the DNA triple helix by stereoselective intramolecular cyclization and olefin metathesis.
abstract: Canonical recognition of gene sequences would allow precise means for specific genetic intervention. Unfortunately, specific recognition of two of the four possible base pairs by triplex-forming oligonucleotide (TFO) as X x T-A and Y x C-G within a triplex currently remains elusive. A series of C1-ethenyl nucleosides have been devised and evaluated extensively for stability and specificity by molecular dynamics simulation. A synthesis via olefin metathesis of the unprotected heterocycle and a conveniently prepared anomerically pure C1-vinyl 2-deoxyribofuranose is presented as a significant improvement over a previously reported strategy.
authors.affiliation: Division of Experimental Therapeutics, Department of Medicine, Columbia University Medical Center, 630 West 168th Street, New York, New York 10032, USA. jhr21@columbia.edu
authors.forename: Jeffrey H
authors.initials: JH
authors.lastname: Rothman
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D020029:Base Pairing; D003500:Cyclization; D004247:DNA / Q000737:chemistry* / Q000378:metabolism*; D006571:Heterocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism; D009705:Nucleosides / Q000138:chemical synthesis* / Q000737:chemistry / Q000378:metabolism; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D000475:Alkenes; D006571:Heterocyclic Compounds; D009705:Nucleosides; C051802:triplex DNA; D004247:DNA