Lok C M, Ward J P, van Dorp D A
Chem Phys Lipids. 1976 Mar;16(2):115-22. doi: 10.1016/0009-3084(76)90003-7.
A method for synthesizing chiral glycerides starting from L- or D-serine is described. Optically-active serine (both enantiomers are commerically available) was transformed into glyceric acid by stereospecific diazotization. The configuration at carbon atom 2 was maintained during the reaction. The glyceric acid was then converted into optically pure isopropylideneglycerol - which is an important intermediate in the synthesis of mono-, di- and triglyderides - by esterification followed by acetalization with acetone and reduction with lithium aluminium hydride. Reaction of this intermediate with triphenylphosphine in tetrachloromethane followed by acid-catalysed hydrolysis and dehydrohalogenation provided optically-active glycidol (2,3-epoxy-1-propanol). The epoxy ring of an ester of glycidol and a fatty acid was then opened stereospecifically with retention of configuration by heating the glycidol ester in the presence of a second fatty acid and a catalyst. This yielded a chiral 1,3-diglyceride which could be converted into a chiral triglyceride.
描述了一种从L-或D-丝氨酸出发合成手性甘油酯的方法。光学活性丝氨酸（两种对映体均可商购）通过立体专一性重氮化转化为甘油酸。反应过程中碳原子2处的构型得以保持。然后，甘油酸通过酯化反应，接着与丙酮进行缩醛化反应并用氢化铝锂还原，转化为光学纯的异亚丙基甘油——这是合成单甘油酯、二甘油酯和三甘油酯的重要中间体。该中间体与三苯基膦在四氯化碳中反应，随后进行酸催化水解和脱卤化氢反应，得到光学活性缩水甘油（2,3-环氧-1-丙醇）。然后，通过在第二种脂肪酸和催化剂存在下加热缩水甘油酯，使缩水甘油酯与脂肪酸的酯的环氧环立体专一性开环并保持构型。这产生了一种手性1,3-二甘油酯，其可转化为手性三甘油酯。
