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Efficient syntheses of (−)-crinine and (−)-aspidospermidine, and the formal synthesis of (−)-minfiensine by enantioselective intramolecular dearomative cyclization

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Abstract

Polycyclic alkaloids bearing all-carbon quaternary centers possess a diversity of biological activities and are challenging targets in natural product synthesis. The development of a general and asymmetric catalytic method applicable to the efficient syntheses of a series of complex polycyclic alkaloids remains highly desirable in synthetic chemistry. Herein we describe an efficient palladium-catalyzed enantioselective dearomative cyclization which is capable of synthesizing two important classes of tricyclic nitrogen-containing skeleton, chiral dihydrophenanthridinone and dihydrocarbazolone derivatives bearing all-carbon quaternary centers, in excellent yields and enantioselectivities. The P-chiral monophosphorus ligand AntPhos is crucial for the reactivity and enantioselectivity, and the choice of the N-phosphoramide protecting group is essential for the desired chemoselectivity. This method has enabled the enantioselective total syntheses of three distinctive and challenging biologically important polycyclic alkaloids, specifically a concise and gram-scale synthesis of (−)-crinine, an efficient synthesis of indole alkaloid (−)-aspidospermidine and a formal enantioselective synthesis of (−)-minfiensine.

Graphical abstract: Efficient syntheses of (−)-crinine and (−)-aspidospermidine, and the formal synthesis of (−)-minfiensine by enantioselective intramolecular dearomative cyclization

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Publication details

The article was received on 26 Apr 2017, accepted on 30 Jun 2017 and first published on 03 Jul 2017


Article type: Edge Article
DOI: 10.1039/C7SC01859B
Citation: Chem. Sci., 2017, Advance Article
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    Efficient syntheses of (−)-crinine and (−)-aspidospermidine, and the formal synthesis of (−)-minfiensine by enantioselective intramolecular dearomative cyclization

    K. Du, H. Yang, P. Guo, L. Feng, G. Xu, Q. Zhou, L. W. Chung and W. Tang, Chem. Sci., 2017, Advance Article , DOI: 10.1039/C7SC01859B

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