烷基取代的双膦配体与金属具有的络合催化反应

烷基取代的双膦配体与金属具有的络合催化反应

催化反应

选用氮杂苯并降冰片烯和二苯基膦氢作为模板进行研究。经过大量的筛选和优化，确定Pd(OAc)2是的金属前体，发现烷基取代的双膦配体与金属具有的络合，可实现的对映选择性控制（可以克服产物自催化导致的反应ee值下降）。同时发现加入Fe(OAc)2,可以的氢化开环的副产物，以及少量的对映选择性。对溶剂温度等因素进行筛选，确定较优条件，在温度70℃下反应6h，可获得97%收率和99% ee。

不同取代基底物在该反应中都表现，得到一些列Azaphos产物。二芳基膦上的基团对ee有的影响（强吸电子CF3基团的二芳基膦，ee降至87％），但氮杂苯并降冰片烯的底物变化保持的手性控制（98-99％ee）。氮杂苯并降冰片烯中氮原子上的取代基团会影响产物收率，当使用Ts代替Boc时，ee值仍然保持99% ee，收率降低至68％。

受氮杂苯并降冰片烯不对称膦氢化的反应的鼓舞，同时也研究了氧杂苯并降冰片烯底物。Pd(OAc)2和(R,R)-QuinoxP组成的较优催化体系也展现出了很好的活性和手性控制及的底物适用性。我们也进行克级反应，仍然表现出的收率和对映选择性(86% yield，90% ee）。虽然与Azaphos系列的产物相比，氧杂苯并降冰片烯产物的对映选择性略低，但的产物很容易的重结晶，继而将ee到> 99％，得到光学纯的产物Oxaphos可直接作为配体使用。

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上述产品齐岳生物均可供应！

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