通过后期镍催化的环氧化物-炔烃还原环化反应全合成箭毒蛙毒素209F和251D。
Total synthesis of pumiliotoxins 209F and 251D via late-stage, nickel-catalyzed epoxide-alkyne reductive cyclization.
作者信息
Woodin Katrina S, Jamison Timothy F
机构信息
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
出版信息
J Org Chem. 2007 Sep 14;72(19):7451-4. doi: 10.1021/jo071132e. Epub 2007 Aug 14.
Abstract
Pumiliotoxins 209F and 251D were synthesized using highly selective nickel-catalyzed epoxide-alkyne reductive cyclizations as the final step. The exocyclic (Z)-alkene found in the majority of the pumiliotoxins was formed stereospecifically and regioselectively, without the use of a directing group on the alkyne, and the epoxide underwent ring opening exclusively at the less hindered carbon to provide the requisite tertiary alcohol. The epoxides were prepared using diastereoselective addition of a sulfoxonium anion to a proline-derived methyl ketone.
摘要
使用高度选择性的镍催化环氧化物-炔烃还原环化反应作为最后一步，合成了箭毒蛙毒素209F和251D。大多数箭毒蛙毒素中发现的环外（Z）-烯烃是立体专一性和区域选择性形成的，炔烃上无需使用导向基团，并且环氧化物仅在位阻较小的碳上开环，以提供所需的叔醇。环氧化物是通过将锍鎓阴离子非对映选择性地加成到脯氨酸衍生的甲基酮上制备的。
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本文引用的文献
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2
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Chem Pharm Bull (Tokyo). 2004 Sep;52(9):1082-5. doi: 10.1248/cpb.52.1082.
3
Nickel-catalyzed reductive cyclizations and couplings.镍催化的还原环化反应和偶联反应。
Angew Chem Int Ed Engl. 2004 Jul 26;43(30):3890-908. doi: 10.1002/anie.200300634.
4
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J Am Chem Soc. 2003 Jul 9;125(27):8076-7. doi: 10.1021/ja0361401.
5
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Chem Rev. 1997 Oct 1;97(6):2341-2372. doi: 10.1021/cr960411r.
6
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Chem Rev. 1996 Feb 1;96(1):505-522. doi: 10.1021/cr950021p.
7
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Chem Rev. 2000 Aug 9;100(8):2741-70. doi: 10.1021/cr9902704.
8
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