Highly diastereoselective synthesis of 2'-deoxy[2'-2H]ribonucleoside derivatives by the use of tris(trimethylsilyl)[2H]silane.
The use of (Me3Si)3SiH or (Me3Si)3Si2H-Et3B system in place of Bu3SnH or Bu3Sn2H-Et3B system for a reductive protylation or deuteration reaction of 2'-Br-2'-deoxy-3',5'-O-TIPDS-[2'-2H]ribonucleosides or 2'-Br-2'-deoxy-3',5'-O-TIPDS-ribonucleosides was confirmed to improve the reactions to afford an excellent diastereoselectivity, i.e., the diastereoselectivity of (2'S)- or (2'R)-2'-deoxy-[2'-2H]ribonucleosides obtained by the reaction at 0 degree C is equivalent to the diastereoselectivity obtained by that using Bu3SnH or Bu3Sn2H-Et3B system at < -70 degrees C; the reductive deuteration of 2'-O-phenoxythiocarbonyl-3',5'-O-TIPDS-ribonucleosides through (Me3Si)3Si2H-Et3B system at 0 degree C also gave (2'R)-2'-deoxy[2'-2H]ribonucleosides with such a high diastereo-selectivity as above.
Kawashima
E
E
Laboratory of Pharmaceutical Chemistry, School of Pharmacy, Tokyo University of Pharmacy and Life Science, Japan.
Uchida
S
S
Ishido
Y
Y
D003853:Deoxyribonucleosides / Q000138:chemical synthesis* / Q000737:chemistry; D003903:Deuterium; D007202:Indicators and Reagents; D007553:Isotope Labeling / Q000379:methods; D015394:Molecular Structure; D012821:Silanes; D013237:Stereoisomerism; D014297:Trimethylsilyl Compounds
D003853:Deoxyribonucleosides; D007202:Indicators and Reagents; D012821:Silanes; D014297:Trimethylsilyl Compounds; D003903:Deuterium