Organic Chemistry

(Dana P.) #1
Section 27.16 Laboratory Synthesis of DNA Strands 065

are not needed. However, the yields are not as good. The H-phosphonate monomers
are activated by reacting with an acyl chloride, which converts them into phosphoan-
hydrides. The group of the nucleoside attached to the solid support reacts with
the phosphoanhydride, forming a dimer. The DMTr protecting group is removed
with acid under mild conditions, and a second activated monomer is added.
Monomers are added one at a time in this way until the strand is complete. Oxidation
with (or tert-butyl hydroperoxide) converts the H-phosphonate groups to phos-
phate groups. The base-protecting groups are removed by aqueous ammonia as in the
phosphoramidite method.


I 2

5 ¿-OH

O

O

O

O−

DMTr O base Pr

an H-phosphonate

activated monomer

solid support

solid support

H P

O

O

O

O

DMTr O
base Pr

O

O

base Pr

H P

solid support

O

O

O

O

base Pr

O

O

base Pr

H P

O

O

O

O

O

DMTr O base Pr
O

O

base Pr

H P

R CCl

O

CR

HO

HO

solid support

O

O

O

O

base Pr

O

O

base Pr

H P

O

O

O

O

base Pr

H P

HO

H+

chain extension


  1. activated monomer

  2. H+


5 ′-OH group

a phosphoanhydride
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