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Please login or sign up for a free trial to access the full content. Dihydroxyacetone Phosphate from Dihydroxyacetone

DOI: 10.1055/sos-SD-202-00363

Clapés, P.; Fessner, W. -D.Science of Synthesis: Stereoselective Synthesis, (20112685.

The biochemical route to dihydroxyacetone phosphate (1) is based on enzymatic phosphoryl transfer to dihydroxyacetone (10, DHA) by ATP-dependent kinases with in situ cofactor regeneration. This procedure gives a product that can either be isolated in relatively high purity (8090%) or used in situ. Three approaches are described in the literature (Schemes 68). In the first approach (Scheme 6), which shows the synthesis of d-tagatose 1,6-bisphosphate (11), glycerol kinase (EC accepts dihydroxyacetone (10) as a substrate analogue.[‌22‌,‌23‌] The reaction includes a cofactor-recycling scheme using 2-(phosphonooxy)prop-2-enoic acid (12) (or acetyl phosphate) as the ultimate phosphoryl donor and can be scaled up efficiently to the mole scale without difficulty. The enzymatic procedure using 2-(phosphonooxy)prop-2-enoic acid (12) as the ultimate phosphorylating agent is somewhat more convenient because 2-(phosphonooxy)prop-2-enoic acid (12) has greater stability in solution than acetyl phosphate. The procedures are otherwise comparable. The disadvantages are the need for a separate preparation of the phosphate donor [2-(phosphonooxy)prop-2-enoic acid or acetyl phosphate], and complications arising during the purification of aldol adducts from the side products released stoichiometrically during ATP regeneration (pyruvate or acetate).[‌24‌,‌25‌]

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Mee eeeee eeeeeeee (Meeeee 8) ee eeeee ee eee eeeeeee ee eee eeee eeeeeeeeeee eeee Meeeeeee eeeeeeee (MeeM-Me) ee eeeeeeeeeeeee eeeeeeeeeeeeeeee (88) eeeee eeeeeeeeeee eeeeeeeeeeeee (MMe) ee eee eeeeeeeee eeeee.[‌88‌] Meeeeeeeeeeeeeee eeeeeeeee (8) eeeeeeeee ee eeee eee ee eeee eee ee eeeeeee eeeeeeeee eeeee eeeeeeee eeeeeeee. Mee eeeeee eee eeeeeeeeeeee eeee eeeeee ee eee eeeeeeeee ee 8,8-eeeeeee-e-eeeee-eee-8-eeeee (88) eeeee eeeeeeee 8,8-eeeeeeeeeeee eeeeeeee (MeeM) eeee eeeeee eeeeee (MMMM). Me eeeeeeeeeee eeeeeee ee eeee eeeeeeee ee eeee eee eeeeeeeeeee eeeee ee ee eeee ee eee eee eeeeee eeeeeeeeeeeeee eeeee eeeeee ee ee eeeeee eeeeeeeee eeeeee ee eeeeeeeeeeeee eee eeeeeeeee eeeeeeeeeeeeeeee (88) ee eeeeeeeeeeeeeeee eeeeeeeee (8). Meeee, eee eeeeeee eeeeeeeee eee eeeeeeeeeeeeeeee eeeee eeeeee ee eee eee, ee eeeeeee eeeeeeeee ee eeeee eeeeeeee ee eeee eeeeeeeeeeeeeeee (88).

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Meeeeeeeeeee Meeeeeeee

Meeeeeee(eeeeeeeeeeeeeeeeee) Meee ee e-Meeeeeee 8,8-Meeeeeeeeeee (88):[‌88‌,‌88‌]

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(M)-8,8-Meeeeee-8-(eeeeeeeeeeeeee)-8-eeeeee-e-eeeee-eee-8-ee-8-eeeee 8-Meeeeeeee (88); Meeeeee Meeeeeeee:[‌88‌]

MMM (88; 888ee, 8eeee), eeeeee eeeeeeeee eeeeeee eeeeeeeee eeee (8.8e, 8eeee), MeMM8 (88ee, 8.88eeee), MMMM (88 M), eee MM (888 M) eeee eeeeeeeee ee e 8.88M MMMMM eeeeee eeee (88eM, eM8.8). MMM eeeeeeee eeee eeeeeee (888ee, 8.8eeee) eee eeeee, eee eee eeeeeeee eeeeeee. Meee MMMM eeeeeeeeeeee eee >88%, eee eM eee eeeeeeee ee 8.8, eee eeeee 8-eeeeee-8-eeeeee-8-eeeeee (888ee, 8.8eeee) eee MeeM eeee eeeeee eeeeee (MMMM, 888 M) eeee eeeee. Meeee 8e ee eeeeeeee, ee eeeeeeeeee eeeeee ee MeeM (888 M) eee eeeee. Mee eeeeeeeeeeee ee eee eeeeeee eee eeeeeeee eeeee eee eeeee-eeeee eeeeeeee ee eee eeeeeeee (8.88 M) (eee eeeee). Mee eeeeeee eee eeeeeeee eeeeeee eeeeee eeeeee eee eeeeeeee ee MMMM ee e Meeeeeeeeeee Mee88 eeeeee (88×8.88ee; eeeeeeee eeeeeeee 8µe) eeeee eeeeeeeee eeeeeee (M: 8.8% e/e MMM ee M8M; M: MeMM; 88% M eeeeee 8eee, 8.8eM·eee8, MM eeeeeeeee 888ee); eeeee: 88%; [α]M88 8.88 (e 8.8, M8M). Mee eeeeee ee MMMM (8) eeeeee eee eeeeeeeeee ee eeeeeeeee eeeee eeeee ee eee eeeeeeeee ee MMMM (8), eeeeeeeee ee α-eeeeeeeeeeeeeeee eeeeeeeeeeeee (α-MMM) eeee eeeeeeeeeee eeeeeeeee ee MMMM ee MMM+, eeeeeeeeee eee eeeeeeee ee eeeeeeeeee ee 888ee. Mee eeeeee eeee eee ee ee, eeeeeeeee eee eeeeeeeeee ee 888ee eee 88eee ee e eeeeeee (8eM) eeeeeeeeee eee eeeeeeee eeeeeee, 8.88M Meee-MMe eM8.8 eeeeee, MMMM eeeeeeeeeee eeee (8.88ee, 8.8µeee), eee α-MMM/MMM (8 M). Mee eee eeeeeeeeeee ee eee MMM eeeeeeeeeee, MMMM (8.888 M), MMM eeeeeeee eeee (8.8ee, 8µeee), eee MeMM8 (8.88ee, 8.88µeee) eeee eeeee ee eee eeeeeee.

8,8-Meeeeee-e-eeeee-eee-8-eeeee (88); Meeeeee Meeeeeeee:[‌88‌]

MeMMM (88.88ee, 8eeee), MMM (88; 888.8ee, 8eeee), Me8M8M8M8 (MMe; 888ee, 8.8eeee), eee MeeM eeee eeeeee eeeeee (MMMM, 88 eeeee) eeee eeeeeeeee ee e 8.8M eeeeeee eeeeee eeee (88eM, eM8.8). MeeM-Me (8µM, 88µe·eM8, 88M·ee8[‌88‌]) eee eeeee eee eee eeeeeee eee eeeeee ee 88°M. Meeee 8e eee 8e, eeeeeeeeee MMe (888e, 8.8eeee) eee eeeee, eee eee eM eee eeeeeeee ee 8.8 eeee 8M MeMM. Meeeeeeeeeeeeeeee ee eee eeeee eeeeee eeeeeee eee eeeeeeee eeeee 88e. Mee eeee eee eeeeee-eeeee, eee eee eeeeeee eee eeeeeeeee eeee MeMM eeeeeeeee). Mee eeeeeeeee eeeeeeeee eeeee eeee eeeeeee ee eeeeeeeeee, eee eee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Meeeeeeeeeee eee eeeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/MeMM 88:8). Mee eeeeeee eee eeeeeeee ee eeee eeeeee eee; eeeee: 88ee (88% eeeee ee MeMMM); >88% eeee ee MMMM.