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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′-tetrahydro-[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 °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)° and 77.9(1)°; the C-P-P internal angles of the five-membered rings of 9 were 90.88(6)° and 93.02(6)° 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 2λ-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 2λ-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-三甲基硅烷基氧基-1,2,1'，2'-四氢-[1,1']双磷酸基的新型重排（7）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]二磷脂（9）和3,4,3'，4'-四叔丁基-[1,1']二磷杂环丁烷基-2,2'-二酮（10）至2,3,6,7-四叔丁基-在150 mm的温度下于0.1 mm真空中升华时，观察到四氢-[1,2]二膦基[1,2-a] [1,2]二磷脂-1，5-二酮（12）。四元环的C-P-C内角反映了（7）中的空间应变，分别为71.9（2）°和77.9（1）°;重新排列后，五元环9的C-P-P内角为90.88（6）°和93.02（6）°。 7与金属铯的反应提供了3,4-二叔丁基-3,4-二氢磷酸-2-醇的铯盐（15），这是2λ-3-phospha-1的第一个例子-烯醇盐并入四元环。由于铯阳离子的尺寸较大，它与2λ-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。化合物7、9、10、12和15的邻位决定了化合物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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