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This direct protocol for introduction of the S-cyanoethyl ether was completely unsuccesful with 4-thio2́-deoxyuridine. Under a wide variety of conditions with 4-thio-2́-deoxyuridine we observed consumption of 3-bromopropionitrile without production of the corresponding thioether, indicating that the alkylation was followed by a facile retro Michael reaction to liberate acrylonitrile under the basic reaction conditions (see reference 9)
-
This direct protocol for introduction of the S-cyanoethyl ether was completely unsuccesful with 4-thio2́-deoxyuridine. Under a wide variety of conditions with 4-thio-2́-deoxyuridine we observed consumption of 3-bromopropionitrile without production of the corresponding thioether, indicating that the alkylation was followed by a facile retro Michael reaction to liberate acrylonitrile under the basic reaction conditions (see reference 9).
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note
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2O, 1:1) to afford 12 and 13, respectively. (formula presented)
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For the successful use of a bis-electrophile in cross-linking reactions, see reference 3
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For the successful use of a bis-electrophile in cross-linking reactions, see reference 3.
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(1976)
Handbook of Biochemistry and Molecular Biology, Nucleic Acids
, vol.1
, pp. 589
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Fasman, G.D.1
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47
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0343095729
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For the origin and design of this side-chain, see reference 3
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For the origin and design of this side-chain, see reference 3.
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48
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0343095730
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All synthetic and post-synthetically modified oligonucleotides were prepared as described in the Experimental Section, and were purified by RP-HPLC to homogeneity
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All synthetic and post-synthetically modified oligonucleotides were prepared as described in the Experimental Section, and were purified by RP-HPLC to homogeneity.
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