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具有季碳中心的环戊烯基氨基酸的对映选择性制备。

Enantioselective Preparation of Cyclopentene-Based Amino Acids with a Quaternary Carbon Center.

作者信息

Franc Michael, Měrka Pavel, Císařová Ivana, Veselý Jan

机构信息

Department of Organic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 43 Praha 2, Czech Republic.

Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 43 Praha 2, Czech Republic.

出版信息

J Org Chem. 2024 Nov 15;89(22):16522-16530. doi: 10.1021/acs.joc.4c01764. Epub 2024 Oct 29.

DOI:10.1021/acs.joc.4c01764
PMID:39471381
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11574854/
Abstract

Azlactone is an important starting material for synthesizing amino acids containing a quaternary α-carbon. In this study, we have developed a sequential "one-pot" procedure involving an enantioselective spirocyclization reaction followed by acidic azlactone opening, which led to amino acid derivatives. The key step of this procedure is a spirocyclization between propargylated azlactones and enals by using a cooperative catalytic approach that combines chiral secondary amine and achiral Pd(0) complexes. The final acid opening of the azlactone motif allows isolation of the corresponding amino acid derivatives as major diastereoisomers in yields ranging from 37% to 70% with enantioselectivities of 85-97% ee. These synthesized amino acid derivatives hold great potential in the pharmaceutical and bioactive compound industries. Moreover, the final amino acid products with a cyclopentene moiety can be further derivatized, opening up even more possibilities for their application.

摘要

氮杂内酯是合成含有季碳α-碳的氨基酸的重要起始原料。在本研究中，我们开发了一种连续的“一锅法”程序，该程序涉及对映选择性螺环化反应，随后是酸性氮杂内酯开环，从而得到氨基酸衍生物。该程序的关键步骤是通过结合手性仲胺和非手性Pd(0)配合物的协同催化方法，使炔丙基化氮杂内酯与烯醛之间发生螺环化反应。氮杂内酯基序的最终酸开环使得能够以37%至70%的产率和85-97% ee的对映选择性分离出相应的氨基酸衍生物作为主要非对映异构体。这些合成的氨基酸衍生物在制药和生物活性化合物行业具有巨大潜力。此外，具有环戊烯部分的最终氨基酸产物可以进一步衍生化，为其应用开辟了更多可能性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c54/11574854/0aa5c351338a/jo4c01764_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c54/11574854/b61117913381/jo4c01764_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c54/11574854/3433fbe84625/jo4c01764_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c54/11574854/e5589440128c/jo4c01764_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c54/11574854/5976654b87f0/jo4c01764_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c54/11574854/0aa5c351338a/jo4c01764_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c54/11574854/b61117913381/jo4c01764_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c54/11574854/3433fbe84625/jo4c01764_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c54/11574854/e5589440128c/jo4c01764_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c54/11574854/5976654b87f0/jo4c01764_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9c54/11574854/0aa5c351338a/jo4c01764_0006.jpg

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本文引用的文献

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