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A convenient method for removal of the t-butyl group from nucleoside bis(t-butyl) phosphates under non-acidic conditions

✍ Scribed by Mitsuo Sekine; Shin Iimura; Takeshi Nakanishi


Publisher
Elsevier Science
Year
1991
Tongue
French
Weight
248 KB
Volume
32
Category
Article
ISSN
0040-4039

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✦ Synopsis


A new method for selective removal of the t-butyl group from 3'bis(t-butyl) phosphate esters of 5'-O-(4,4'-dimethoxytrityl)deoxyribonucleosides was developed by use of Me&iCl and Et=N. Several unexpected properties of the t-butyl group were described.

Quite recently, Johnslez has reported di-t-butyl N,N-diethylphosphoramidite (BEPA) as a new phosphitylating agent for phosphorylation of alcohols. This reaction gave cleanly bis(t-butyl) alkyl phosphates in high yields. However, its removal for conversion to unesterified monoalkyl phosphates required rather drastic acidic conditions such as 1 M HCl/dioxanc, r.t., 4 hl and 6-90 % trifluoroacetic acid/benzene or CH2C11, r.t., 24 h."-" This is only a drawback when the t-butyl group is considered to be used as an phosphate protecting group in the synthesis of acid-sensitive natural products containing phosphates.