Chemical and enzymatic syntheses of 6-deoxyhexoses. Conversion to 2,5-dimethyl-4-hydroxy-2,3-dihydrofuran-3-one (Furaneol) and analogs
Chemical and enzymatic syntheses of 6-deoxyhexoses. Conversion to 2,5-dimethyl-4-hydroxy-2,3-dihydrofuran-3-one (Furaneol) and analogs
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DOI：
10.1021/jo00168a023
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发表时间：
1983-10
影响因子：
3.6
通讯作者：
Chi‐Huey Wong;F. Mazenod;G. Whitesides
中科院分区：
文献类型：
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作者：
Chi‐Huey Wong;F. Mazenod;G. Whitesides
当用醛缩酶和磷酸丙糖异构酶处理含有D-果糖1，6-二磷酸（FDP）和D-乳醛的溶液时，形成6-脱氧-D-果糖1-磷酸（6-脱氧F-1-P）。这种转变涉及三个反应：醛缩酶催化的FDP裂解为磷酸二羟丙酮和磷酸D-甘油醛的混合物，磷酸丙糖异构酶催化的磷酸二羟丙酮和磷酸D-甘油醛的平衡，和醛缩酶催化的磷酸二羟丙酮和D-乳醛缩合为6-脱氧F-1-P。类似的方法将FDP和L-乳醛的混合物转化为6-脱氧山梨糖1-磷酸（6-脱氧S-1-P）。单独制备的磷酸二羟丙酮与D-乳醛经醛缩酶催化反应直接生成6-脱氧F-1-P;磷酸二羟丙酮与α-羟基丁醛经类似反应生成6-甲基-6-脱氧己糖1-磷酸的混合物。磷酸糖的酸催化水解释放出相应的游离糖。通过二羟基丙酮和D，L-乳醛的碱催化羟醛缩合直接形成含有6-脱氧己糖的混合物。用酸处理任何6-脱氧己糖产生2，5-二甲基-4-羟基-2，3-二氢呋喃-3-酮（呋喃酮，风味成分）。也可以通过在碱性介质中氢解FDP和其它己糖磷酸盐以中等产率制备呋喃酮
6-Deoxy-D-fructose 1-phosphate (6-deoxyF-1-P) forms when a solution containing D-fructose 1,6-diphosphate (FDP) and D-lactaldehyde is treated with the enzymes aldolase and triosephosphate isomerase. This transformation involves three reactions: aldolase-catalyzed cleavage of FDP to a mixture of dihydroxyacetone phosphate and D-glyceraldehyde phosphate, triosephosphate isomerase catalyzed equilibration of dihydroxyacetone phosphate and D-glyceraldehyde phosphate, and aldolase-catalyzed condensation of dihydroxyacetone phosphate and D-lactaldehyde to 6-deoxyF-1-P. An analogous process converts a mixture of FDP and L-lactaldehyde to 6-deoxysorbose 1-phosphate (6-deoxyS-1-P). Aldolase-catalyzed reaction of dihydroxyacetone phosphate, prepared separately, with D-lactaldehyde yields 6-deoxyF-1-P directly; similar reaction of dihydroxyacetone phosphate with α-hydroxybutyraldehyde yields a mixture of 6-methyl-6-deoxyhexose 1-phosphates. Acid-catalyzed hydrolysis of the sugar phosphates releases the corresponding free sugars. A mixture containing 6-deoxyhexoses is formed directly by base-catalyzed aldol condensation of dihydroxyacetone and D,L-lactaldehyde. Treatment of any of the 6-deoxyhexoses with acids generates 2,5-dimethyl-4-hydroxy-2,3-dihydrofuran-3-one (Furaneol, a flavor principle). Furaneol can also be prepared in moderate yields by hydrogenolysis of FDP and other hexose phosphates in alkaline media