An 8-step, gram-scale synthesis of the (-)-sparteine surrogate (22 % yield, with just 3 chromatographic purifications) and a 10-step, gram-scale synthesis of (-)-sparteine (31 % yield) are reported. Both syntheses proceed with complete diastereocontrol and allow access to either antipode. Since the syntheses do not rely on natural product extraction, our work addresses long-term supply issues relating to these widely used chiral ligands.
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http://dx.doi.org/10.1002/anie.201710261 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Zhejiang Uiversity, Chemistry, 866 Yuhangtang Road, 310058, Hangzhou, CHINA.
Heck silylation of unactivated alkenes is an efficient strategy for the synthesis of useful organosilicon compounds. However, extensive efforts have been dedicated to only achieving achiral molecules. Herein, a highly regio- and enantioselective cobalt-catalyzed Heck silylation of unactivated alkenes with hydrosilanes is reported for the first time, providing access to axially chiral alkenes in good to excellent yields with 87-98% ee.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Tirupati, Tirupati 517619, India.
Diastereoselective synthesis of -3,4-difunctionalized tetrahydroquinoline and chromane derivatives via the oxo-sulfonylation of 1,7-enynes is demonstrated. The reaction involves a three-component oxidative radical polar crossover (ORPC) approach wherein a vinyl carbocation intermediate undergoes nucleophilic substitution to afford the corresponding keto functional group. Deprotection of the N-Ts group, gram-scale synthesis, and other synthetic applications were illustrated.
View Article and Find Full Text PDFOrg Lett
January 2025
Pfizer Oncology Medicinal Chemistry, 10770 Science Center Drive, San Diego, California 92121, United States.
General procedures for the rhodium-catalyzed annulation of aryl/heteroaryl -pivaloyl hydroxamic acids and norbornadiene have been developed. Employing norbornadiene as an acetylene equivalent enables utilization of diverse heterocyclic substrates for this transformation which fail to react or undergo competitive Lossen rearrangement under previously reported conditions. Microwave heating significantly reduces reaction times compared to conventional protocols and allows a one-step process to be realized.
View Article and Find Full Text PDFOrg Lett
January 2025
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215123, P. R. China.
The azahelicenes are structurally fascinating and practically useful chiral scaffolds, but their synthesis, especially in a catalytically asymmetric manner, is rather challenging. Herein, we report a CPA-catalyzed transfer hydrogenation process, which enables a rapid kinetic resolution of aza[6]helicenes. The established strategy provides facile access to enantioenriched aza[6]helicenes and tetrahydro[6]helicenes from easily available starting materials.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Jiangsu Key Laboratory of Pesticide Science and Department of Chemistry, College of Sciences, Nanjing Agricultural University, Nanjing 210095, P. R. China.
A strategy for trifluoroacetylation of quinoxaline-2(1)-ones has been investigated. This strategy employs masked trifluoroacyl reagents to obtain trifluoroacetylated quinoxaline-2(1)-ones under metal-, catalyst-, and light-free conditions. This approach is distinguished by its functional group compatibility and tolerance, as well as the simplicity of the experimental process, making it suitable for gram-scale synthesis.
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