Synthesis of enantiopure phthalides including 3-butylphthalide, a fragrance component of celery oil, and determination of their absolute configurations
Synthesis of enantiopure phthalides including 3-butylphthalide, a fragrance component of celery oil, and determination of their absolute configurations
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DOI：
10.1002/chir.20156
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发表时间：
2005-05-05
期刊：
影响因子：
2
通讯作者：
Hiroi, K
中科院分区：
文献类型：
--
作者：
Kosaka, M;Sekiguchi, S;Hiroi, K
对映体纯苯酞 2 和 5-8 通过相应的醇与樟脑磺胺二氯邻苯二甲酸手性助剂 (1S,2R,4R)-(-)-CSDP 酸 3 进行对映拆分，然后用 KOH 在 MeOH 中溶剂解，并用铱络合物 28 催化氧化手性二醇。苯酞 2 和 5-8 的绝对构型通过应用以下公式确定： M α NP 酸(4)、2-甲氧基-2-(1-萘基)丙酸与手性合成前体醇的 H-1-NMR 各向异性方法。在3-苯基苯酞(R)-(-)-7的情况下，通过使用MαNM酸4的H-1-NMR各向异性方法测定的绝对构型与通过X射线晶体学方法测定的绝对构型一致。通过应用这些方法，以对映体纯形式合成了芹菜精油的香料成分3-丁基苯酞(S)-(-)-2，并明确确定了其绝对构型。手性 17:218-232, 2005。(c) 2005 Wiley-Liss, Inc.
Enantiopure phthalides 2 and 5-8 were synthesized via enantioresolution of the corresponding alcohols with a chiral auxiliary of camphorsultarn dichlorophthalic acid, (1S,2R,4R)-(-)-CSDP acid 3, followed by solvolysis with KOH in MeOH and the catalytic oxidation of chiral glycols with iridium complex 28. The absolute configurations of phthalides 2 and 5-8 were determined by applying the H-1-NMR anisotropy method of M alpha NP acid (4), 2-methoxy-2-(l-naphthyl)propionic acid, to the chiral synthetic precursory alcohols. In the case of 3-phenylphthalide (R)-(-)-7, the absolute configuration determined by the H-1-NMR anisotropy method using M alpha NM acid 4 agreed with that by the X-ray crystallographic method. By applying these methods, 3-butylphthalide (S)-(-)-2, a fragrance component of essential oil of celery, has been synthesized in an enantiopure form, and its absolute configuration was unambiguously determined. Chirality 17:218-232, 2005. (c) 2005 Wiley-Liss, Inc.