We report a protocol for the highly efficient iridium-catalyzed asymmetric hydrogenation of racemic α-substituted lactones dynamic kinetic resolution. Using Ir-SpiroPAP ()- as a catalyst, a wide range of chiral diols were prepared in a high yield (80-95%) with a high enantioselectivity (up to 95% ee) under mild reaction conditions. This protocol was used for enantioselective syntheses of (-)-preclamol and a chiral 2,5-disubstituted tetrahydropyran.
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http://dx.doi.org/10.1039/c6sc04609f | DOI Listing |
J Am Chem Soc
January 2025
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China.
Functional group-directed site- and enantioselective C(sp)-H functionalization of alcohols or masked alcohols represents a formidable challenge. We herein report the first example of iridium-catalyzed asymmetric α-C(sp)-H borylation of primary alcohol-derived carbamates by the judicious choice of directing groups. A variety of chiral borylated carbamates were obtained with good to high enantioselectivities.
View Article and Find Full Text PDFChem Commun (Camb)
December 2024
Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Department of Chemistry and Medi-X Pingshan, Southern University of Science and Technology, Shenzhen 518055, People's Republic of China.
The iridium-catalyzed asymmetric hydrogenation of α-alkoxy-β-ketoesters dynamic kinetic resolution has been achieved with high efficiency and enantioselectivity. This strategy allows for the synthesis of differentiated -1,2-diol derivatives in high yields, exhibiting excellent enantio- and diastereoselectivity (up to 99% yield, 99% ee, and 99 : 1 dr). Additionally, high turnover number (TON) experiments (up to 1000 TON) and gram-scale synthesis of a key fragment of the potential drug Tesaglitazar were successfully performed, highlighting the protocol's potential for broader applications.
View Article and Find Full Text PDFOrg Lett
December 2024
Institute for Research in Biomedicine (IRB Barcelona), Barcelona Institute of Science and Technology (BIST), Baldiri Reixac 10, 08028 Barcelona, Spain.
J Am Chem Soc
December 2024
Department of Chemistry, Shenzhen Grubbs Institute, Southern University of Science and Technology, Shenzhen 518000, China.
A catalytic protocol for the iridium-catalyzed asymmetric hydrogenation (AH) of γ- or δ-hydroxy ketones to rapidly assemble various aliphatic enantioenriched tetrahydrofurans (THFs) or tetrahydropyrans (THPs) is disclosed. A wide range of enantioenriched THFs or THPs were obtained in high yields and excellent enantioselectivities (up to 99% and up to 96.5:3.
View Article and Find Full Text PDFOrg Lett
December 2024
Institute for Advanced and Applied Chemical Synthesis, College of Pharmacy, State Key Laboratory of Bioactive Molecules and Druggability Assessment, Guangdong Province Key Laboratory of Pharmacodynamic Constituents of TCM & New Drugs Research, Jinan University, Guangzhou 510632, Guangdong, China.
This paper describes an iridium-catalyzed allylation of ring-fused pyrazolones that proceeds with excellent regio-, diastereo- and enantio-selectivities. The approach exploits unactivated, racemic allylic alcohols as a source of allyl building blocks. Asymmetric syntheses of a series of biologically relevant, chiral pyrazolones highlight the utility of the methodology.
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