P-chiral phosphinoselenoic chlorides and phosphinochalcogenoselenoic acid esters: Synthesis, characterization, and conformational studies
P-chiral phosphinoselenoic chlorides and phosphinochalcogenoselenoic acid esters: Synthesis, characterization, and conformational studies
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DOI：
10.1021/jo0484979
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发表时间：
2005-02-04
影响因子：
3.6
通讯作者：
Murai, T
中科院分区：
文献类型：
--
作者：
Kimura, T;Murai, T
通过 PhPCl2 与格氏试剂和元素硒反应得到对手性烷基或芳基苯基膦硒酰氯。用两种不同的格氏试剂和元素硒处理 PCl3 也获得了对手性二烷基氯化物。通过X射线分子结构分析确定氯化物的结构。通过用碱金属醇盐和硫属醇化物处理氯化物合成了带有P=Se双键的对手性膦基硫属硒酸酯，而带有P-Se单键的那些氯化物则通过用氢氧化钠、硫化物或硒化物和烷基碘依次处理氯化物得到。酯的 X 射线分子结构分析表明它们采用左构象。计算结果支持观察到的构象偏好。模型化合物的自然键轨道分析表明，两种类型的非键轨道相互作用，n(E') --> sigma*(P=E) 和 n(E) --> sigma*(P-E')，在这些化合物中很重要。在实验的 Se-77 NMR 化学位移或酯中 P-Se 键的耦合常数与模型化合物的计算 P-Se 键长之间观察到线性相关性。
P-Chiral alkyl or aryl phenylphosphinoselenoic chlorides were obtained by reacting PhPCl2 with Grignard reagents and elemental selenium. P-Chiral dialkyl chlorides were also obtained by treating PCl3 with two different Grignard reagents and elemental selenium. The structure of the chloride was determined by X-ray molecular structure analysis. P-Chiral phosphinochalcogenoselenoic acid esters bearing a P=Se double bond were synthesized by treating the chlorides with alkali metal alkoxide and chalcogenolates, whereas those bearing a P-Se single bond were obtained by sequential treatment of the chlorides with sodium hydroxide, sulfide or selenide, and alkyl iodides. X-ray molecular structure analyses of esters showed that they adopted gauche conformations. The computational results supported the observed conformational preference. Natural bond orbital analyses of the model compounds showed that two types of nonbonding orbital interactions, n(E') --> sigma*(P=E) and n(E) --> sigma*(P-E'), are important in these compounds. Linear correlations were observed between the experimental Se-77 NMR chemical shifts or the coupling constants of P-Se bonds in the esters and the calculated P-Se bond lengths of the model compounds.