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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >A rearrangement of 1,1-linked four-membered rings to bicyclic bridgehead five-membered rings: A phosphorus turn
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A rearrangement of 1,1-linked four-membered rings to bicyclic bridgehead five-membered rings: A phosphorus turn

机译：将1,1连接的四元环重排为双环桥头五元环：磷转

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摘要

Novel rearrangements of 2,3,2',3'-tetra-tert-butyl-4,4'-bis-trimethylsilanyloxy-1,2,1',2'tetrahy dro-[1,1'] biphosphetyl (7) to 1,2,5,6-tetra-tert-butyl-3,7-bis-trimethylsilanyloxy-1H,5H-[1,2] diphospholo-[1,2-a][1,2] diphosphole (9) and of 3,4,3',4'-tetra-tert-butyl-[1,1'] biphosphetanyl-2,2'-dione (10) to 2,3,6,7-tetra-tert-butyl-tetrahydro-[1,2] diphospholo-[1,2-a][1,2] diphosphole-1,5-dione (12) were observed during sublimation at 150 degrees C in 0.1 mm vacuum. The C-P-C internal angles of the four-membered rings, which reflect steric strain in (7), were 71.9(2)degrees and 77.9(1)degrees; the C-P-P internal angles of the five-membered rings of 9 were 90.88(6)degrees and 93.02(6)degrees after rearrangement. Reaction of 7 with metallic caesium provided the caesium salt of 3,4-di-tert-butyl-3,4-dihydro-phosphet-2-ol (15), which is the first example of a 2 lambda-3-phospha-1-enolate being incorporated into four-membered ring. Due to its large size, the caesium cation has a rare coordination mode with both the phosphorus and oxygen atoms of the 2 lambda-3-phospha-1-enolate, forming infinite polymeric chains in the solid state of 15. Two tert-butyl groups in the vicinal positions of compounds 7, 9, 10, 12 and 15 dictate the "gauche" conformations in compounds 7, 9, 10, 12 and 15, enforcing this stereoselectivity around the C-C-C portion of the rings in the enlargement reaction.
机译：2,3,2'，3'-四叔丁基-4,4'-双三甲基甲硅烷基氧基-1,2'，1'，2'四氢-dro [[1,1']双磷酸基（7）的新型重排到1,2,5,6-四叔丁基-3,7-双三甲基甲硅烷基氧基-1H，5H- [1,2]二膦基-[1,2-a] [1,2]二膦酸酯（9）和3,4,3'，4'-四叔丁基-[1,1']二磷杂环烷基-2,2'-二酮（10）至2,3,6,7-四叔丁基-在150摄氏度，0.1毫米真空升华过程中观察到四氢-[1,2]二磷-[1,2-a] [1,2]二磷-1,5-二酮（12）。反映（7）中的空间应变的四元环的C-P-C内角分别为71.9（2）度和77.9（1）度。重新排列后，五元环9的C-P-P内角为90.88（6）度和93.02（6）度。 7与金属铯的反应提供了3,4-二叔丁基-3,4-二氢-磷酸-2-醇（15）的铯盐，它是2 lambda-3-phospha- 1-烯酸酯被结合到四元环中。由于铯阳离子的尺寸较大，因此它与2 lambda-3-phospha-1-enolate的磷和氧原子均具有罕见的配位模式，在15的固态下形成无限的聚合物链。两个叔丁基化合物7、9、10、12和15的邻位中的“ Cauche”构象决定了化合物7、9、10、12和15中的“ gauche”构象，从而在扩大反应中在环的CCC部分周围增强了这种立体选择性。

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