2-甲氧基-2-(1-萘基)丙酸酯的结晶构象。

Enantiomer Pub Date : 2002-07-01 DOI:10.1080/10242430212879
Takuma Fujita, S. Kuwahara, Masataka Watanabe, N. Harada
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引用次数: 15

摘要

采用(S)-(+)-2-甲氧基-2-(1-萘基)丙酸(MalphaNP酸1)对1,2,3,4-四氢-4-苯酚(4)进行对映拆分。外消旋醇(+/-)-4与(S)-(+)-1酯化,形成的非对映体酯混合物在硅胶上用高效液相色谱分离,得到第一洗脱的酯5a和第二洗脱的酯5b。用LiAlH4还原酯5a,得到对映纯醇(+)-4。对酯5a单晶进行x射线晶体学分析,确定其绝对构型为(S,S),并将S绝对构型赋值为(+)-4。x射线分析中最引人注目的发现是,即使在结晶状态下,甲氧基氧原子也与酯羰基氧原子同步。这正是在1H NMR各向异性方法中假设的MalphaNP酸酯的首选构象。(+)-4的S绝对构型也通过CD和1H NMR各向异性方法得到了证实。
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Crystalline state conformation of 2-methoxy-2-(1-naphthyl)propionic acid ester.
The enantioresolution method using (S)-(+)-2-methoxy-2-(1-naphthyl)propionic acid (MalphaNP acid 1) was applied to 1,2,3,4-tetrahydro-4-phenanthrenol (4). Racemic alcohol (+/-)-4 was esterified with (S)-(+)-1, and a diastereomeric mixture of esters formed was separated by HPLC on silica gel giving the first-eluted ester 5a and the second-eluted one 5b. Ester 5a was reduced with LiAlH4 yielding enantiopure alcohol (+)-4. A single crystal of ester 5a was subjected to X-ray crystallography to determine its absolute configuration as (S,S), and therefore to assign the S absolute configuration to (+)-4. The most striking finding in the X-ray analysis is that the methoxyl oxygen atom is syn to the ester carbonyl oxygen even in the crystalline state. This is just the preferred conformation of MalphaNP acid esters assumed in the 1H NMR anisotropy method. The S absolute configuration of (+)-4 was also confirmed by the CD and 1H NMR anisotropy methods.
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