Kodali D R
J Lipid Res. 1987 Apr;28(4):464-9.
Optically active 1- or 3-acyl-sn-glycerols were synthesized from 2,3- or 1,2-isopropylidene-sn-glycerols, respectively. The 2,3- or 1,2-isopropylidene-sn-glycerols were condensed with appropriate long saturated or unsaturated fatty acids and the resulting acyl isopropylidene compounds were treated with dimethylboronbromide at - 50 degrees C to give the title compounds. The ketal cleavage of acyl isopropylidene-sn-glycerols by dimethylboronbromide to produce the long 1- or 3-acyl-sn-glycerols was effective and gave good yields (70-90%). The reaction conditions were mild and there was no acyl migration, as shown by optical rotation of the monoacyl-sn-glycerols. The synthesis of 2,3-isopropylidene-sn-glycerol was improved to give an overall yield of 40% from L-arabinose. L-Arabinose was first converted to its 1,1'-diethylmercapto derivative and then condensed with 2-methoxypropene to yield 1,1'-diethyl-mercapto-4,5-isopropylidene-L-arabinose. Oxidation of this compound with sodium periodate followed by reduction with sodium borohydride under alkaline conditions yielded 2,3-isopropylidene-sn-glycerol [alpha]22D = -14.90 degrees, neat (Lit. 8 [alpha]22D = -14.5 degrees, neat; 14 [alpha]25D = -10.8 degrees; methanol C, 16.9). The optical purity of isopropylidene-sn-glycerols was determined as benzoyl derivatives on a high performance liquid chromatographic column packed with a chiral stationary phase.
旋光性1-或3-酰基-sn-甘油分别由2,3-或1,2-异亚丙基-sn-甘油合成。将2,3-或1,2-异亚丙基-sn-甘油与适当的长链饱和或不饱和脂肪酸缩合，所得酰基异亚丙基化合物在-50℃下用二甲基硼溴处理，得到标题化合物。二甲基硼溴对酰基异亚丙基-sn-甘油进行缩酮裂解以生成长链1-或3-酰基-sn-甘油是有效的，且产率良好（70-90%）。反应条件温和，单酰基-sn-甘油的旋光性表明不存在酰基迁移。2,3-异亚丙基-sn-甘油的合成得到改进，以L-阿拉伯糖计总产率为40%。L-阿拉伯糖首先转化为其1,1'-二乙硫基衍生物，然后与2-甲氧基丙烯缩合，得到1,1'-二乙硫基-4,5-异亚丙基-L-阿拉伯糖。该化合物用过碘酸钠氧化，然后在碱性条件下用硼氢化钠还原，得到2,3-异亚丙基-sn-甘油[α]22D = -14.90°，纯品（文献值8[α]22D = -14.5°，纯品；14[α]25D = -10.8°；甲醇中C，16.9）。异亚丙基-sn-甘油的光学纯度在手性固定相填充的高效液相色谱柱上以苯甲酰衍生物测定。
