PubMed · 9074870
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1997. An alternative to methyl bromide.. https://pubmed.ncbi.nlm.nih.gov/9074870/
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In this study, carbon tetrabromide (CTB), bromoform (BF) and dibromomethane (DBM) were the target compounds investigated for their reduction kinetics and pathways with nano-scale Fe and Ni/Fe particles synthesized in laboratory. The BET surface areas of these nano-scale particles were around two orders of magnitude higher than that of the commercial micro-scale Fe particles. Batch reduction experiments were carried out with a metal loading of 2.5gl(-1) for the nano-scale particles, and 125gl(-1) for the commercial micro-scale Fe. The nano-scale Ni/Fe was the most reactive for reductive dehalogenation of the brominated methanes. The rates of bromide ion liberated during the reduction of the brominated methanes were usually higher than the disappearance rates of the parent compounds, indicating occurrence of concerted debromination mechanism. Analysis of the reduction kinetics showed that CTB and BF were mainly reduced through hydrogenolysis reaction, while over 76% of DBM was reduced through concerted reductive debromination to methane. Addition of Ni to Fe increased the specific reduction rates of the target compounds and reactive intermediates, but only marginally changed the distribution of their end products. Through comprehensive kinetic and mechanistic examinations of the reduction dehalogenation of various brominated methanes, a scheme summarizing their overall reduction pathways with the nano-scale Fe and Ni/Fe is proposed.
A novel modular, efficient, and practical methodology of preparation of 6-substituted pyridin-2-yl C-nucleosides was developed. An addition of 2-lithio-6-bromopyridine 2b to TBDMS-protected 2-deoxyribonolactone 5 gave aduct 7 as an equilibrium mixture of anomeric hemiketals 1-(6-bromopyridin-2-yl)-1-hydroxynucleosides 7a,b and its open form 7c. Reduction of the adduct 7 with Et3SiH and BF3 x Et2O afforded the desired 6-bromonucleoside 8a as pure beta-anomer in a total yield of 32% over two steps from 5. Intermediate 8a was then subjected to a series of palladium catalyzed cross-coupling reactions and aminations to give a series of protected 1beta-(6-alkyl-, 6-aryl-, and 6-aminopyridin-2-yl)-2-deoxyribonucleosides 9. Catalytic hydrogenation of 8a gave an unsubstituted pyridine C-nucleoside, and diazotative oxodeamination of 6-aminopyridine nucleoside 9f by isopentyl nitrite in acetic acid gave 6-oxopyridine nucleoside 10i. Deprotection of silylated nucleosides 9 by Et3N.3HF gave a series of free C-nucleosides 10.
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