維基百科

雙㗁唑啉配位基

雙㗁唑啉配位基(英語：bisoxazoline ligands)是一類含有雙㗁唑啉環的C2對稱性手性配位基。最簡單的雙㗁唑啉配位基以一個亞甲基（-CH2-）橋連雙㗁唑啉環，簡稱為BOX；通過吡啶環連接㗁唑啉的配位基十分常用，簡稱為PyBOX。含雙㗁唑啉配位基的錯合物主要被用於不對稱催化中。

歷史

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雙㗁唑啉配位基的發展

1984年Brunner等人首次將㗁唑啉配位基用於不對稱催化，連同許多席夫鹼，進行對映選擇性的類卡賓環丙烷化反應[1]。席夫鹼是當時的主要配位基，如野依良治在1968年發現不對稱催化的過程中就使用了席夫鹼[2]，其同事Tadatoshi Aratani[3]在1970年代發表的多篇使用席夫鹼的對映選擇性環丙烷化的論文在隨後深刻地影響了Brunner的工作[4][5][6]。 最初㗁唑啉配位基的ee僅為4.9%，相比於席夫鹼配位基的65.6%表現不佳。隨後Brunner在研究二醇的單苯基化過程中重新研究了㗁唑啉配位基，並發展出了手性吡啶㗁唑啉配位基，其ee在1986年報道時為30.2% [7]，在1989年時達到了45% [8]。同年Pfaltz等人報道了使用C2對稱的半咕啉配位基進行的對映選擇性卡賓環丙烷化反應，ee值達到了92-97% [9]，但此類配位基的缺點是需要多步進行合成，且產率低，約為30% [10]。

 
C2對稱軸向手性的雙㗁唑啉配位基

到了1989年Nishiyama等人在Brunner工作的基礎上發展出了第一個雙㗁唑啉配位基，合成了PyBOX配位基用於酮的矽氫化反應，ee高達93% [11]。一年後，Masamune等人報道了第一個BOX配位基[12]並首次用於銅催化的類卡賓環丙烷化反應，在1%莫耳負載量下實現高達99%的ee，該項工作引起了人們對BOX家族的極大興趣。至彼時由於2-㗁唑啉環的合成已經十分成熟[13] [14]，相關研究進展迅速[15][16] [17]。這些研究主要基於經典的BOX和PyBOX配位基，並出現了許多替代結構[18][19]。


合成

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㗁唑啉環的合成已經十分完備，一般通過2-胺基醇與合適的官能基關環來進行。合成雙㗁唑啉配位基時，最好使用含雙官能基的起始原料，以期在同一步構建雙環。二腈與二羧酸類化合物是最常使用的原料，被用於生產絕大多數的雙㗁唑啉配位基。

 

BOX和PyBOX的廣泛應用，可能有它們能夠從丙二腈和吡啶二甲酸開始非常方便地構建雙㗁唑啉環的原因，分子的手性一般在此步由胺基醇引入。

應用

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催化

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一般而言，對於BOX配位基，立體化學結構與預期的扭曲平面正方形分子構型中間體一致[20][21]。㗁唑啉4號位上的取代基阻擋了底物一側的對映面，使產物有對映選擇性。該方法可以用於羥醛反應 [22]，並能推廣到多種反應，包括但不限於曼尼希反應 [23]、烯反應 [24]、麥可加成 [25]、納扎羅夫環化反應 [26]和雜原子狄爾斯-阿爾德反應 [27]等。

 
BOX對映選擇性範例

另一方面，攜有徑向的三齒PyBOX配位基與底物路易斯酸的兩點鍵合形成了四方錐形的結構，以苄氧基乙醛作親電試劑為例，立體化學結果顯示羰基氧在赤道面結合，醚氧在四方錐軸向結合[28]。

 
PyBox Stereochemical model

含雙㗁唑啉的錯合物可以用於各種不對稱催化之中，其電中性的特性使其適合與貴金屬一起使用[29][30][31]，但最常見的是與銅的錯合物[30]。

構建碳-碳鍵

編輯

雙㗁唑啉配位基的一個重要應用是構建碳-碳鍵，對一系列的不對稱環加成反應有效，最初在類卡賓的構建環丙烷體系的反應中被引入，例如西蒙斯–史密斯反應 [12]，並拓展到1,3-偶極環加成反應和狄爾斯-阿爾德反應之中。

 
BOX參與的羥醛反應[32]
 
BOX參與的D-A反應[33]:合成馬鞭草烯酮，最後含DPPA的轉化過程包括改性的庫爾提斯重排反應。

其他

編輯

與環丙烷化類似，雙㗁唑啉可以用於氮丙啶化；另一個常見的反應是矽氫化（英語：HydrosilylationHydrosilylation）反應，最初在PyBOX的使用中被引入[11]。其它的利基應用有作氟化催化劑[34]和瓦克爾法環化等[35]。

 
對映選擇性矽氫化[11]

參見

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參考文獻

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