Highly enantioselective iridium catalyzed carbonyl (2-vinyl)allylation or "isoprenylation" is achieved via hydrogen auto-transfer or 2-propanol-mediated reductive coupling from primary alcohol or aldehyde reactants, respectively. Using this method, asymmetric total syntheses of the terpenoid natural products (+)-ipsenol and (+)-ipsdienol were achieved.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6339811 | PMC |
| http://dx.doi.org/10.1039/c8cc09706b | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Heteroaryl-Directed Iridium-Catalyzed Enantioselective C-H Alkenylations of Secondary Alcohols.
J Am Chem Soc
December 2024
Department of Chemistry, University of Liverpool, Crown Street, Liverpool L69 7ZD, United Kingdom.
Under iridium-catalyzed conditions, 2-aza-aryl-substituted secondary alcohols undergo C(sp)-H addition reactions to alkynes to provide alkenylated tertiary alcohols. The processes occur with very high regio- and enantioselectivity. An analogous addition to styrene is shown to provide a prototype C(sp)-H alkylation process.
View Article and Find Full Text PDFEnantioselective α-C(sp)-H Borylation of Masked Primary Alcohols Enabled by Iridium Catalysis.
J Am Chem Soc
December 2024
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 PDFFacile access to chiral -1,2-diol derivatives Ir-catalyzed asymmetric hydrogenation of α-alkoxy-β-ketoesters.
Chem 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 PDFSynthesis of γ-Amino Amides by Iridium-Catalyzed Enantioselective Hydroamination of Internal Alkenes Directed by an Amide.
Angew Chem Int Ed Engl
December 2024
Tsinghua University, Department of Chemistry, 1 Tsinghua Yuan, 100084, Beijing, CHINA.
Catalytic regio- and enantioselective hydroamination of less activated internal alkenes presents a challenge to synthetic chemists due to their low reactivity and the difficulty in simultaneously controlling regio- and enantioselectivities. Here, we report an iridium-catalyzed enantioselective hydroamination of internal alkenes directed by an amide. The amide group on the alkene effectively directs the catalyst to overcome the low reactivity and control the regioselectivity and the enantiotopic face selection.
View Article and Find Full Text PDFHighly Enantioselective Synthesis of 3,3-Diarylpropyl Amines and 4-Aryl Tetrahydroquinolines via Ir-Catalyzed Asymmetric Hydrogenation.
Org Lett
December 2024
Institute for Research in Biomedicine (IRB Barcelona), Barcelona Institute of Science and Technology (BIST), Baldiri Reixac 10, 08028 Barcelona, Spain.
Article Synopsis
- Chiral nitrogen-containing compounds are essential in various industries, but their synthesis can be challenging due to a vast range of chemical possibilities.
- This research details a selective method to create 3,3-diarylallyl phthalimides, which, when treated with iridium catalysts, transform into 3,3-diarylpropyl amines with very high enantioselectivity (98-99% ee).
- The study highlights the role of alkene purity in achieving high enantioselectivity and illustrates how the resulting chiral propylamines can be used to make important bioactive drugs like tolterodine and tolpropamine.
Want AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!