一價銠金屬/掌性雙環雙烯配基錯合物催化環狀α,β-不飽和氮-磺醯基酮亞胺與有機硼試劑進行高鏡像選擇性及高位性選擇性的不對稱加成反應
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2017
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Abstract
本論文敘述以一價銠金屬和掌性雙環雙烯配基形成錯合物為催化劑，催化有機硼試劑與亞胺，進行具位像選擇性及鏡像選擇性的不對稱加成反應。
使用一價銠金屬和掌性雙環雙烯配基L6a形成的錯合物為催化劑，以1,4-二噁烷為溶劑碳酸鉀為添加劑，催化芳香基硼酸與α,β-不飽和亞胺21，進行不對稱1,4-加成反應，產物22產率最高可達95%，鏡像超越值最高可達99% ee。
以一價銠金屬和掌性雙環雙烯配基L1a形成的錯合物為催化劑，以乙腈為溶劑水為添加劑，進行烯丙基三氟硼酸鉀鹽對亞胺21的1,2-加成反應，產物32產率最高可達99%，鏡像超越值最高可達99.5% ee。
A highly enantioselective and regioselective addition of organo boron reagents to cyclic α,β-unsaturated N-sulfonyl ketimines catalyzed by in situ generated Rh (Ι) catalyst is described. The 1,4-addition reaction of arylboronic acids proceeds with excellent regioselectivity to offer 1,4 adducts in good yields (up to 95% yield) and stereoselectivity (up to 99% ee) in the presence of Rh (Ι) catalyst. Futhermore, in the presence of Rh(Ι)/L1a the enantioselective allyation of cyclic N-sulfonyl ketimine of 21 proceeds via 1,2-addition fashion, offering the corresponding products in up to 99% yield and 99.5% ee.
A highly enantioselective and regioselective addition of organo boron reagents to cyclic α,β-unsaturated N-sulfonyl ketimines catalyzed by in situ generated Rh (Ι) catalyst is described. The 1,4-addition reaction of arylboronic acids proceeds with excellent regioselectivity to offer 1,4 adducts in good yields (up to 95% yield) and stereoselectivity (up to 99% ee) in the presence of Rh (Ι) catalyst. Futhermore, in the presence of Rh(Ι)/L1a the enantioselective allyation of cyclic N-sulfonyl ketimine of 21 proceeds via 1,2-addition fashion, offering the corresponding products in up to 99% yield and 99.5% ee.
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一價銠金屬, Rh