Science of Synthesis

McKenna, C. E.; Kashemirov, B. A.; Błażewska, K. M., Science of Synthesis, (2009) 42, 812.

The selective hydrolysis of triesters of phosphoric acid is a very convenient method for the preparation of dialkyl or diaryl phosphates under mild conditions. This method can be used in the synthesis of oligonucleotides,[‌90‌] caged phosphoproteins,[‌91‌] phospholipids,[‌92‌,‌93‌] and many other types of phosphate diester. Implementation of this approach generally entails the selective removal of a susceptible esterifying group (such as a methyl, tert-butyl, or 2-cyanoethyl) group from the triester. The tert-butyl group can be easily removed by treatment with trifluoroacetic acid.[‌91‌] Triethylamine and butylamine are convenient nucleophiles for the demethylation of phosphoric acid triesters,[‌93‌] and a sterically hindered primary amine (tert-butylamine) is effective for the elimination of the 2-cyanoethyl group from oligonucleotide triester intermediates.[‌94‌] When two 2-cyanoethyl groups are present, as for example in phosphate triester ‌93‌, only one is normally removed by the amine base to give the product, e.g. ‌94‌ (‌Scheme 30‌).[‌92‌]

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‌Meeeee 88‌ Meeeeeeee Meeeeeeeeeee[‌88‌]

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8-Meeeeeeeee (8M,8M,8M)-8-(Meeeeeeeee)-8-eeeeeeeeeeeeee-8-eeee Meeeeeeee (‌88‌):[‌88‌]

M 88% eeee ee e-MeMM8 ee MM8Me8 eee eeeee ee eeeee eee(8-eeeeeeeeee) eeeeeeee ‌88‌, eee eee eeeeeee eee eeeeeee ee ee eee 8 e, eeeeeeeeeeee ee eeeeeee, eee MeMMe eee eeeee eeeeeeee ee MeMM (8 eM). Mee eeeeeee eeeee eee eeeeee eeee M8M eee eeeee, eeee eeeee (Me8MM8). Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, MMMe8/MeMM/MeMM 88:88:8); eeeee: 88%.

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) 88/8, 888.
• 8.Meeeee-Meee, (8888) 88/8, 888.
• 8.Meeeee-Meee, (8888) 88/8, 888.
• 8.Meeeee-Meee, (8888) M 8, 888.