Desai T, Gigg J, Gigg R, Payne S, Penades S
Laboratory of Lipid and General Chemistry, National Institute for Medical Research, Mill Hill, London, United Kingdom.
Carbohydr Res. 1992 Oct 9;234:1-21. doi: 10.1016/0008-6215(92)85035-x.
Racemic 1,2,4-tri-O-benzyl-5,6-O-isopropylidene-myo-inositol was prepared by a new route involving crotyl (but-2-enyl) ethers and converted into the (-)-omega-camphanates to give the pure crystalline 1L-diastereoisomer and the chirally impure, syrupy 1D-diastereoisomer. The latter was converted via the 1-O-allyl or 1-O-p-methoxybenzyl ethers into chirally pure 1D-2,3,6-tri-O-benzyl-myo-inositol [required as an intermediate for the synthesis of 1D-myo-inositol 1,4,5-trisphosphate (1,4,5-IP3)], which was also prepared by de-p-methoxybenzylation of 1D-2,3,6-tri-O-benzyl-1,5-di-O-p-methoxybenzyl-myo-inositol. Racemic 2,4-di-O-benzyl-5,6-O-isopropylidene-1-O-p-methoxybenzyl-myo-inositol was prepared in a similar way to the analogous tribenzyl ether (using crotyl ethers) and the omega-camphanate esters behaved similarly, allowing efficient resolution by crystallisation of the (-)- and (+)-omega-camphanates. Racemic 1,2,4-tri-O-allyl-3-O-(but-2-enyl)-myo-inositol was resolved via the (-)-omega-camphanates and was also converted into 1,2,4-tri-O-(cis-prop-1-enyl)-myo-inositol, an alternative intermediate for the synthesis of 1,4,5-IP3.
外消旋1,2,4-三-O-苄基-5,6-O-异亚丙基-myo-肌醇通过一条涉及巴豆基（丁-2-烯基）醚的新路线制备，并转化为（-）-ω-樟脑酸酯，得到纯结晶的1L-非对映异构体和手性不纯的糖浆状1D-非对映异构体。后者通过1-O-烯丙基或1-O-对甲氧基苄基醚转化为手性纯的1D-2,3,6-三-O-苄基-myo-肌醇[作为合成1D-myo-肌醇1,4,5-三磷酸酯（1,4,5-IP3）的中间体所需]，其也通过1D-2,3,6-三-O-苄基-1,5-二-O-对甲氧基苄基-myo-肌醇的脱对甲氧基苄基化制备。外消旋2,4-二-O-苄基-5,6-O-异亚丙基-1-O-对甲氧基苄基-myo-肌醇以与类似的三苄基醚（使用巴豆基醚）相似的方式制备，并且ω-樟脑酸酯的行为类似，允许通过（-）-和（+）-ω-樟脑酸酯的结晶进行有效拆分。外消旋1,2,4-三-O-烯丙基-3-O-（丁-2-烯基）-myo-肌醇通过（-）-ω-樟脑酸酯拆分，并且也转化为1,2,4-三-O-（顺式丙-1-烯基）-myo-肌醇，这是合成1,4,5-IP3的另一种中间体。
