烷基取代的雙膦配體與金屬具有的絡合催化反應

催化反應

選用氮雜苯并降冰片烯和二苯基膦氫作為模板進行研究。經過大量的篩選和優(yōu)化，確定Pd(OAc)2是的金屬前體，發(fā)現烷基取代的雙膦配體與金屬具有的絡合，可實現的對映選擇性控制（可以克服產物自催化導致的反應ee值下降）。同時發(fā)現加入Fe(OAc)2,可以的氫化開環(huán)的副產物，以及少量的對映選擇性。對溶劑溫度等因素進行篩選，確定較優(yōu)條件，在溫度70℃下反應6h，可獲得97%收率和99% ee。

不同取代基底物在該反應中都表現，得到一些列Azaphos產物。二芳基膦上的基團對ee有的影響（強吸電子CF3基團的二芳基膦，ee降至87％），但氮雜苯并降冰片烯的底物變化保持的手性控制（98-99％ee）。氮雜苯并降冰片烯中氮原子上的取代基團會影響產物收率，當使用Ts代替Boc時，ee值仍然保持99% ee，收率降低至68％。

受氮雜苯并降冰片烯不對稱膦氫化的反應的鼓舞，同時也研究了氧雜苯并降冰片烯底物。Pd(OAc)2和(R,R)-QuinoxP組成的較優(yōu)催化體系也展現出了很好的活性和手性控制及的底物適用性。我們也進行克級反應，仍然表現出的收率和對映選擇性(86% yield，90% ee）。雖然與Azaphos系列的產物相比，氧雜苯并降冰片烯產物的對映選擇性略低，但的產物很容易的重結晶，繼而將ee到> 99％，得到光學純的產物Oxaphos可直接作為配體使用。

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