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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis of P-stereogenic diarylphosphinic amides by directed lithiation: transformation into tertiary phosphine oxides via methanolysis, aryne chemistry and complexation behaviour toward zinc(II)
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Synthesis of P-stereogenic diarylphosphinic amides by directed lithiation: transformation into tertiary phosphine oxides via methanolysis, aryne chemistry and complexation behaviour toward zinc(II)

机译：定向锂化合成P-立体异构二芳基次膦酰胺：通过甲醇分解，芳烃化学和对锌（II）的络合行为转变为叔膦氧化物

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摘要

The highly diastereoselective synthesis of P-stereogenic phosphinic amides via directed ortho lithiation (DoLi) of (S-C)-P,P-diphenylphosphinic amides with t-BuLi followed by electrophilic quench reactions is described. Functionalised derivatives containing a wide variety of ortho substituents (Cl, Br, I, OH, N-3, SiMe3, SnMe3, P(O)Ph-2, Me, allyl, (BuOCO)-Bu-t) have been prepared in high yields with diastereomeric ratios up to 98 : 2. The X-ray diffraction structure of the ortho-stannylated and ortho-iodo compounds showed that the pro-S P-phenyl ring was stereoselectively ortho-deprotonated by the organolithium base. The usefulness of the method is supported by two key transformations, the synthesis of P-stereogenic methyl phosphinates through replacement of the chiral auxiliary by a methoxy group and the first example of the insertion of benzyne into the P-N bond of a P-stereogenic phosphinic amide. A DFT study of this reaction showed that the insertion proceeds through a [2 + 2] cycloaddition and a subsequent ring-opening with retention of the P-configuration. Explorative coordination chemistry of the new P-stereogenic ligands provided access to a chiral phosphinic amide-phosphine oxide Zn(II) complex, the crystal structure of which is reported.
机译：描述了通过（S-C）-P，P-二苯基次膦酰胺的定向邻位锂化（DoLi）与t-BuLi的高非对映选择性合成P-立体异构的次膦酰胺，然后进行亲电猝灭反应。含有多种邻位取代基（Cl，Br，I，OH，N-3，SiMe3，SnMe3，P（O）Ph-2，Me，烯丙基，（BuOCO）-Bu-t）的官能化衍生物已于2007年制备。非对映异构体比例高达98：2的高收率。邻甲锡烷基化和邻碘化合物的X射线衍射结构表明，前S P-苯环被有机锂碱立体选择性地邻去质子化。该方法的实用性得到了两个关键的转化的支持：通过用甲氧基取代手性助剂来合成P-立体生成的次膦酸酯，以及第一个将苯炔插入P-立体生成的次膦酰胺的PN键中的例子。 。 DFT研究表明，该插入过程是通过[2 + 2]环加成反应和随后的开环并保留P-构型而进行的。新的P-立体异构配体的探索性配位化学提供了接触手性次膦酰胺-氧化膦Zn（II）配合物的途径，据报道其晶体结构。

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