Homoharringtonine and its congener cephalotaxine were synthesized. Oxidative ring-opening of a furan unveils an amine-tethered dicarbonyl, which undergoes spontaneous transannular Mannich cyclization. The cascade builds the full cephalotaxine substructure in a single operation in 60 % yield. A Noyori reduction enabled synthesis of the title compounds with excellent enantioselectivity (k =278).
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http://dx.doi.org/10.1002/anie.201902174 | DOI Listing |
Waste Manag
December 2024
Key Laboratory of Agro-Environment in Downstream of Yangtze Plain/Scientific Observing and Experimental Station of Arable Land Conservation (Jiangsu), Ministry of Agriculture and Rural Affairs, Institute of Agricultural Resources and Environment, Jiangsu Academy of Agricultural Sciences, Nanjing 210014, China. Electronic address:
Org Biomol Chem
December 2024
Department of Chemistry, Birla Institute of Technology and Science, Pilani 333031, Rajasthan, India.
Construction of a chiral methanamine unit at the C3 position of pyrrole is highly desirable; nevertheless, it remains challenging due to its intrinsic electronic properties. Herein, we present an operationally straightforward and direct asymmetric approach for accessing α-(3-pyrrolyl)methanamines under benign organocatalytic conditions for the first time. The one-pot transformation proceeds smoothly through an amine-catalyzed direct Mannich reaction of succinaldehyde with various -cyclic imines, followed by a Paal-Knorr cyclization with a primary amine.
View Article and Find Full Text PDFOrg Lett
October 2024
Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, Yunnan Key Laboratory of Research and Development for Natural Products, Yunnan Characteristic Plant Extraction Laboratory, School of Pharmacy, Yunnan University, Kunming, Yunnan 650500, P. R. China.
A novel strategy based on a common intermediate bearing a chirality-tunable structure unit for the collective syntheses of corynantheine-type and heteroyohimbine-type alkaloids has been developed. Key transformations of the synthetic strategy are a sequential nucleophilic C-N bond formation/Mannich-type cyclization to construct the highly functional C/D rings, a stereocontrolled introduction of the C15 and C20 chiral centers based on the chirality-tunable structure unit, and an amine-directed addition of MeAl to construct the C18 methyl group.
View Article and Find Full Text PDFMol Divers
September 2024
Department of Chemistry, SRM Institute of Science & Technology, Delhi-NCR Campus, Modinagar, Ghaziabad, 201204, India.
Arborisidine and Arbornamine are two monoterpenoid indole alkaloids that were isolated from the Malayan Kopsia arborea plant. This review provides valuable information about the total and formal syntheses of these alkaloids. The synthesis strategies discussed in this review, such as Pictet-Spengler cyclization, chemo- and stereoselective oxidative cyclization, Michael/Mannich cascade process, and intramolecular N-alkylation, can be useful for developing new methods to synthesize these and other similar compounds.
View Article and Find Full Text PDFJ Org Chem
September 2024
School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou 310018, China.
Herein, a gold-catalyzed alkyne oxidative cyclization/Mannich-type addition cascade reaction of ynamides with 1,3,5-triazinanes in the presence of a Brønsted acid has been presented. A class of functionalized fluorenes bearing a quaternary carbon center was synthesized directly with moderate to excellent yields via in situ formed α-oxo carbenes using quinoline -oxide as the oxidant under mild reaction conditions.
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