Science of Synthesis

McKenna, C. E.; Kashemirov, B. A.; Błażewska, K. M., Science of Synthesis, (2009) 42, 829.

Diethyl or diphenyl (2-oxo-5,5-diphenyloxazolidin-3-yl)phosphonate ‌147‌ (R2 = Et, Ph), readily obtained from 5,5-diphenyloxazolidin-2-one by reaction with the corresponding phosphorochloridate,[‌128‌] can be used in the synthesis of phosphate triesters ‌149‌ (‌Scheme 47‌).[‌127‌,‌128‌] The reagents react either in the presence of butyllithium or in the presence of a copper(II) trifluoromethanesulfonate catalyst, triethylamine, and N,N′-bis[(E)-benzylidene]ethane-1,2-diamine (‌148‌, BEN), a chelating ligand. In both cases, the reaction proceeds well with primary, secondary, and, in contrast to diphenyl phosphorochloridate, tertiary alcohols ‌146‌, as well as with phenols. The butyllithium-based protocol appears to be more efficient for the synthesis of phosphate triesters from diethyl (2-oxo-5,5-diphenyloxazolidin-3-yl)phosphonate (44–97%), whereas the copper(II) trifluoromethanesulfonate system is preferable for reactions with diphenyl (2-oxo-5,5-diphenyloxazolidin-3-yl)phosphonate (46–88%).[‌128‌] Lewis acid catalysis is comparatively mild and is therefore applicable to phosphorylation of some sensitive substrates. The copper(II) trifluoromethanesulfonate catalyzed phosphorylation of adenosine and guanosine leads to 5′-phosphorylated products that are hydrolyzed to give diesters during purification on a silica gel column (water/methanol elution).

‌Meeeee 88‌ Meeeeeeeeeeeeee eeee (8-Mee-8,8-eeeeeeeeeeeeeeeeee-8-ee)eeeeeeeeeeee[‌888‌]

‌Meeeeeeeeee 88‌

M8	M8	Meeee (%)	88M MMMe (δ, MMMe8)	Mee
	Me	88	–88.88	[‌888‌]
	Me	88	–88.88	[‌888‌]
	Me	88	–8.88	[‌888‌]
	Me	88	8.88	[‌888‌]
	Me	88	8.88	[‌888‌]
Me	Me	88	–88.88	[‌888‌]
Me	Me	88	–8.88	[‌888‌]
MM8MM=MM8	Me	88	–88.88	[‌888‌]
MM8MM=MM8	Me	88	–8.88	[‌888‌]
MM8M≡MM	Me	88	–88.8	[‌888‌]
MM8M≡MM	Me	88	–8.88	[‌888‌]
Me	Me	88	–88.88	[‌888‌]
Me	Me	88	–8.88	[‌888‌]
eMe	Me	88	–88.88	[‌888‌]
eMe	Me	88	–8.88	[‌888‌]
e-Me	Me	88	–88.8	[‌888‌]
e-Me	Me	88	–8.88	[‌888‌]
e-Me	Me	88	–88.88	[‌888‌]
e-Me	Me	88	–8.88	[‌888‌]
8-MeM8M8	Me	88	–88.88	[‌888‌]
8-MeM8M8	Me	88	–8.88	[‌888‌]
8-M8MM8M8	Me	88	–88.88	[‌888‌]
8-M8MM8M8	Me	88	–8.88	[‌888‌]
eeeeeee	Me	88	–88.88	[‌888‌]
8-MeMM8M8	Me	88	–88.88	[‌888‌]
8-MeMM8M8	Me	88	–8.88	[‌888‌]

e 888 MMe.

Meeeeeeeeeee Meeeeeeee

Meeeeeee Meeeeeeeee ‌888‌; Meeeeee Meeeeeeee:[‌888‌]

Mee (8-eee-8,8-eeeeeeeeeeeeeeeeee-8-ee)eeeeeeeeeee ‌888‌ (M8 = Me, Me) eee eeeeeeeeeee ee eeeeeeeeeeeeeee ee 8,8-eeeeeeeeeeeeeeeeee-8-eee.[‌888‌]

Mee eeeeeee ‌888‌ (8.8 eeee) eee eeeee ee e eeeeeee eeee ee Me(MMe)8 (8.8 eeee) eee M,M′-eee[(M)-eeeeeeeeeee]eeeeee-8,8-eeeeeee (‌888‌; 8.8 eeee) ee MM8Me8 (88 eM) ee ee eeeee M8. Mee eeee eee eeeeeee ee ee eee 8 eee eeeeee Me8M (8 eeee) eee eee eeeeeeeeeee ‌888‌ (8 eeee) eeee eeeee eeeeeeeeeeee. Mee eeeeeee eee eeee eeeeeee ee ee eee 88 e. Me MM8Me (88 eM) eee eeeee eee eee eeeeeee eee eeeeeeeee eeee MeMMe (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee MeMMM8 (88 eM) eee eeeee (88 eM) eeee eeeee (MeMM8). Mee eeeeeeeee eeeeeeeeee eee eeeeeeee eee eee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeeeee eeeee); eeeee: 88–88%.

References

Meeeeee Meeeeeeeeee

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