Synthesis and Structure of 1,2-Dimethylene[2.10]metacyclophane and Its Conversion into Chiral [10]Benzenometacyclophanes
Synthesis and Structure of 1,2-Dimethylene[2.10]metacyclophane and Its Conversion into Chiral [10]Benzenometacyclophanes
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1,2-二亚甲基[2.10]偏环芳烷的合成、结构及其手性[10]苯偏环芳烷的转化
DOI：
10.1002/ejoc.201601647
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发表时间：
2017
影响因子：
2.8
通讯作者：
Akther T
中科院分区：
文献类型：
--
作者：
Akther T
用苄基三甲基三溴化铵溴化5，21-二叔丁基-8，24-二甲氧基-1，2-二甲基[2.10]间环番-1-烯（MCP-1-烯;1）仅得到1，2-双（溴甲基）-5，21-二叔丁基-8，24-二甲氧基[2.10]MCP-1-烯（2）。2与Zn和AcOH在CH 2Cl 2溶液中室温脱溴24 h，得到稳定的固体化合物二亚甲基[2.10] MCP 7，产率92%。化合物7用乙炔二甲酸二甲酯（DMAD）处理，以良好的产率得到1，2-（3′，6 ′-二氢苯并）-5，21-二叔丁基-8，24-二甲氧基[2.10]MCP-4′，5 ′-二甲基甲酸酯（8）。Diels-Alder加合物8通过与2，3-二氯-5，6-二氰基-1，4-苯醌（DDQ）的芳构化反应转化为具有C1对称性的新型固有手性芳烃桥连二甲氧基[2.10]MCP-4′，5 ′-二甲基羧酸酯9。以7为原料，在甲苯中与N-苯基马来酰亚胺在110 °C反应，再与DDQ芳构化，合成了一种新型的N-苯基马来酰亚胺取代的1，2-（3′，6 ′-二氢苯并）-5，21-二叔丁基-8，24-二甲氧基[2.10]MCP-4′，5 ′-N-苯基马来酰亚胺10。9的单晶X射线分析揭示了非对称异构体的形成。
Bromination of 5,21‐di‐tert‐butyl‐8,24‐dimethoxy‐1,2‐dimethyl[2.10]metacyclophan‐1‐ene (MCP‐1‐ene;1) with benzyltrimethylammonium tribromide exclusively afforded 1,2‐bis(bromomethyl)‐5,21‐di‐tert‐butyl‐8,24‐dimethoxy[2.10]MCP‐1‐ene (2). Debromination of2with Zn and AcOH in CH2Cl2solution at room temperature for 24 h produced dimethylene[2.10]MCP7in 92 % yield, which is a stable solid compound. Compound7was treated with dimethyl acetylenedicarboxylate (DMAD) to provide 1,2‐(3′,6′‐dihydrobenzo)‐5,21‐di‐tert‐butyl‐8,24‐dimethoxy[2.10]MCP‐4′,5′‐dimethylcarboxylate (8) in good yield. Diels–Alder adduct8was converted into a novel and inherently chiral areno‐bridged dimethoxy[2.10]MCP‐4′,5′‐dimethylcarboxylate9, possessingC1symmetry, by aromatization with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ). A new type ofN‐phenyl‐maleimide substituted 1,2‐(3′,6′‐dihydrobenzo)‐5,21‐di‐tert‐butyl‐8,24‐dimethoxy[2.10]MCP‐4′,5′‐N‐phenylmaleimide10was also synthesized from7through treatment withN‐phenylmaleimide in toluene at 110 °C followed by aromatization with DDQ. Single‐crystal X‐ray analysis of9revealed the formation of asyn‐isomer.