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Nucleotides, Part LXVII , The 2‐Cyanoethyl and (2‐Cyanoethoxy)carbonyl Group for Base Protection in Nucleoside and Nucleotide Chemistry
Author(s) -
Merk Claudia,
Reiner Tilman,
Kvasyuk Evgeny,
Pfleiderer Wolfgang
Publication year - 2000
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/1522-2675(20001220)83:12<3198::aid-hlca3198>3.0.co;2-q
Subject(s) - chemistry , nucleobase , guanosine , nucleotide , nucleoside , deoxyguanosine , deoxyadenosine , stereochemistry , deoxyribonucleotide , amide , protecting group , cleavage (geology) , guanine , deamination , nucleic acid , ribonucleoside , carbonyl group , organic chemistry , dna , enzyme , biochemistry , adduct , rna , gene , alkyl , geotechnical engineering , fracture (geology) , engineering
The amino functions of the common 2′‐deoxyribo‐ and ribonucleosides were blocked by the (2‐cyanoethoxy)carbonyl group on treatment with 2‐cyanoethyl carbonochloridate ( 5 ) or 1‐[(2‐cyanoethoxy)carbonyl]‐3‐methyl‐1 H ‐imidazolium chloride ( 6 ) leading to 7 , 18 , 8 , 19 , 9 , and 20 . In 2′‐deoxyguanosine, the amide group was additionally blocked at the O 6 position by the 2‐cyanoethyl (→ 27 ) and 2‐(4‐nitrophenyl)ethyl group (→ 31 , 32 ). Comparative kinetic studies regarding the cleavage of the ce/ceoc and npe/npeoc group by β ‐elimination revealed valuable information about the ease and sequential deprotection of the various blocking groups at different sites of the nucleobases. Besides the 5′‐ O ‐(dimethoxytrityl)‐protected 3′‐(2‐cyanoethyl diisopropylphosphoramidites) 38 and 39 of N 4 ‐[(2‐cyanoethoxy)carbonyl]‐2′‐deoxycytidine and N 6 ‐[(2‐cyanoethoxy)carbonyl]‐2′‐deoxyadenosine, respectively, the N 2 ‐[(2‐cyanoethoxy)carbonyl]‐2′‐deoxy‐ O 6 ‐[2‐(4‐nitrophenyl)ethyl]guanosine analog 40 is recommended as building block for oligo‐2′‐deoxyribonucleotide synthesis.