CHEMISTRY OF ALPHA-AMINONITRILES - ALDOMERISATION OF GLYCOLALDEHYDE PHOSPHATE TO RAC-HEXOSE 2,4,6-TRIPHOSPHATES AND (IN PRESENCE OF FORMALDEHYDE) RAC-PENTOSE 2,4-DIPHOSPHATES - RAC-ALLOSE 2,4,6-TRIPHOSPHATE AND RAC-RIBOSE 2,4-DIPHOSPHATE ARE THE MAIN REACTION-PRODUCTS

被引:181
作者
MULLER, D [1 ]
PITSCH, S [1 ]
KITTAKA, A [1 ]
WAGNER, E [1 ]
WINTNER, CE [1 ]
ESCHENMOSER, A [1 ]
机构
[1] SWISS FED INST TECHNOL,ORGAN CHEM LAB,UNIV STR 16,CH-8092 ZURICH,SWITZERLAND
关键词
D O I
10.1002/hlca.19900730526
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Chemistry of α‐Aminonitriles. Aldomerisation of Glycolaldehyde Phosphate to rac‐Hexose 2,4,6‐Triphosphates and (in Presence of Formaldehyde) rac‐Pentose 2,4‐Diphosphates: rac‐Allose 2,4,6‐Triphosphate and rac‐Ribose 2,4‐Diphosphate Are the Main Reaction Products Glyclaldehyde phosphate aldomerizes in aqueous NaOH solution to a product mixture containing the racemates of the two diastereoisomeric tetrose 2,4‐diphosphates and eight hexose 2,4,6‐triphosphates. At room temperature in the absence of air and after 7 days, a solution 0.08Min glycolaldehyde phosphate (=formylmethyl dihydrogenphosphate)and 2M in NaOH gives products, in up to 80% yield, with a tetrose/hexose derivative ratio of ca 1:10 and with rac‐allose, 2,4,6‐triphosphate comprising up to 50% of the mixture of sugar phosphates. When the reaction is run under the same conditions but in the presence of 0.5 mol‐equiv. of formaldehyde, sugar phosphates are formed in up to 45% yield, with pentose 2,4‐diphosphates now predominating over hexose triphosphates by a ration f 3:1 rac‐Ribose 2,4‐diphosphate is found to be the major component, the ratios am ribose, arabinose, lyxose, and xylose 2,4‐diphosphates being 52:14:23:11 in a representative experiment. The pentose diphosphates are constitutionally stable under the reaction conditions (observed for 23 weeks), but the diastereoisomeric ratios slowly change with time (tc 22:34:30:14 after 23 weeks), showing that ribose 2,4‐diphosphate is not the thermodynamically favored diastereoisomer. The observed product distributions in both the pentose and the hexose series (after 1 week) reveal an aldolization mode that is preferentially erythro in the product‐determining step (the reaction of glycolaldehyde phosphate as its enolate with glycerinaldehyde 2‐phosphate and tetrose 2,4‐diphosphate, respectively). An attempt is made to rationalize both this fact and the kinetic predominance of ribose 2,4‐diphosphate in the pentose series and allose 2,4,6‐triphosphate in the hexose series. Their configuration along the C‐chain can be interpreted as corresponding to a minimum number of 1‐5 repulsions in the packing of phosphate and OH substituents and minimal steric interaction between substituents at the reaction centers in the transition state of the product‐determining step. The aldomerization of glycolaldehyde phosphate in the presence of formaldehyde is a variant of the formose reaction, It avoids the formation of complex formose product mixtures, largely as a consequence of the fact that aldoses which are phosphorylated at the C(2) Copyright © 1990 Verlag GmbH & Co. KGaA, Weinheim
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页码:1410 / 1468
页数:59
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