烷基取代的雙膦配體與金屬具有的絡(luò)合催化反應(yīng)

催化反應(yīng)

選用氮雜苯并降冰片烯和二苯基膦氫作為模板進(jìn)行研究。經(jīng)過(guò)大量的篩選和優(yōu)化，確定Pd(OAc)2是的金屬前體，發(fā)現(xiàn)烷基取代的雙膦配體與金屬具有的絡(luò)合，可實(shí)現(xiàn)的對(duì)映選擇性控制（可以克服產(chǎn)物自催化導(dǎo)致的反應(yīng)ee值下降）。同時(shí)發(fā)現(xiàn)加入Fe(OAc)2,可以的氫化開(kāi)環(huán)的副產(chǎn)物，以及少量的對(duì)映選擇性。對(duì)溶劑溫度等因素進(jìn)行篩選，確定較優(yōu)條件，在溫度70℃下反應(yīng)6h，可獲得97%收率和99% ee。

不同取代基底物在該反應(yīng)中都表現(xiàn)，得到一些列Azaphos產(chǎn)物。二芳基膦上的基團(tuán)對(duì)ee有的影響（強(qiáng)吸電子CF3基團(tuán)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(tuán)會(huì)影響產(chǎn)物收率，當(dāng)使用Ts代替Boc時(shí)，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(duì)稱膦氫化的反應(yīng)的鼓舞，同時(shí)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(xiàn)出了很好的活性和手性控制及的底物適用性。我們也進(jìn)行克級(jí)反應(yīng)，仍然表現(xiàn)出的收率和對(duì)映選擇性(86% yield，90% ee）。雖然與Azaphos系列的產(chǎn)物相比，氧雜苯并降冰片烯產(chǎn)物的對(duì)映選擇性略低，但的產(chǎn)物很容易的重結(jié)晶，繼而將ee到> 99％，得到光學(xué)純的產(chǎn)物Oxaphos可直接作為配體使用。

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