Reduction of Bis(phosphonio)isophosphindolides to Phosphane-Functionalized Benzo[c]phospholides
Reduction of Bis(phosphonio)isophosphindolides to Phosphane-Functionalized Benzo[c]phospholides
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DOI：
10.1002/(sici)1099-0682(199907)1999:7
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发表时间：
1999-07
影响因子：
2.3
通讯作者：
D. Gudat;Volker Bajorat;Stefan Häp;M. Nieger;G. Schröder
中科院分区：
文献类型：
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作者：
D. Gudat;Volker Bajorat;Stefan Häp;M. Nieger;G. Schröder
已发现双（膦酰基）苯并[c]磷酰化物（异磷杂吲哚）1a、B与镁或碱金属萘化物MC10H8（M = Li、Na、K）反应，其中一个或两个膦酰基被还原。主要产物是单或双（膦基）取代的杂环2，3，6，7，其特征在于通过原位NMR研究，并在某些情况下分离。2与过量的[Ni（CO）4]反应得到配合物4，其结构经X射线衍射表征。1a与碱金属的反应遵循更复杂的过程，得到2、3和取代产物8的混合物，其进一步还原为膦基取代的苯并[c]磷脂9。后者可以通过首先用PhNa处理将1a转化为8，然后用锂处理而选择性地形成。讨论了膦取代的苯并[c]磷脂的NMR数据和4的结构特征。
Bis(phosphonio)benzo[c]phospholides (isophosphindolides) 1a,b have been found to react with magnesium or alkali metal naphthalenides MC10H8 (M = Li, Na, K) with reduction of one or both of the phosphonio groups. The main products are the mono- or bis(phosphanyl)-substituted heterocycles 2, 3, 6, 7, which have been characterized by in situ NMR studies and in some cases isolated. Subsequent reaction of 2 with excess [Ni(CO)4] gave the complex 4, which has been characterized by X-ray diffractometry. Reactions of 1a with alkali metals followed a more complicated course and gave a mixture of 2, 3, and the substitution product 8, which was further reduced to the phosphanido-substituted benzo[c]phospholide 9. The latter could be formed selectively by first converting 1a into 8 by treatment with PhNa and then treating this with lithium. NMR data of the phosphane-substituted benzo[c]phospholides and the structural features of 4 are discussed.