The straightforward strategy of building a chiral C-O bond directly on a general carbon radical center is challenging and stereocontrol of the reactions of open-chain hydrocarbon radicals remains a largely unsolved problem. Advance in this elementary step will spur the development of asymmetric radical C-O bond construction. Herein, we report a copper-catalyzed regioselective and enantioselective carboesterification of substituted dienes using alkyl diacyl peroxides as the source of both the carbon and oxygen substituents. The participation of external acids in this reaction substantially extends its applicability and leads to structurally diverse allylic ester products. This work represents the advance in the key elementary reaction of intermolecular enantioselective construction of C-O bond on open-chain hydrocarbon radicals and may lead to the discovery of other asymmetric radical reactions.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8602303 | PMC |
| http://dx.doi.org/10.1038/s41467-021-26843-2 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Catalytic Enantioselective Nucleophilic Amination of α-Halo Carbonyl Compounds with Free Amines.
J Am Chem Soc
December 2024
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Centre for Tissue Restoration & Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR 999077, China.
Catalytic enantioselective substitution of the readily available racemic α-halo carbonyl compounds by nitrogen nucleophiles represents one of the most convenient and direct approaches to access enantioenriched α-amino carbonyl compounds. Distinct from the two available strategies involving radicals and enolate ions, herein we have developed a new protocol featuring an electronically opposite way to weaken/cleave the carbon-halogen bond. A suitable chiral anion-based catalyst enables effective asymmetric control over the key positively charged intermediates.
View Article and Find Full Text PDFVisible-Light Photocatalyzed Skeletal Rearrangement Enables the Synthesis of Highly Functionalized Xanthenes with Antitumor Activity.
Angew Chem Int Ed Engl
December 2024
Jinan University College of Pharmacy, College of Pharmacy, CHINA.
Highly functionalized xanthenes possess an impressive range of bioactivities and daunting synthetic challenge due to their unique ring systems and stereocenters. Here, we report an unprecedented ketyl radicals-induced skeletal rearrangement reaction of spirodihydrobenzofurans, enabled by zero-valent iron as reducing agents via photoredox catalysis, facilitating the facile preparation of various highly functionalized xanthenes. The features of this protocol include high chemo- and regioselectivity, exceptionally mild conditions, a broad substrate scope, scalability to gram-scale quantities, and consistent delivery of good to excellent yields.
View Article and Find Full Text PDFAsymmetric intra and inter-hemispheric subcellular rat brain correlation of arginyl-aminopeptidase activity during development and aging.
Brain Res
December 2024
Department of Physiology, Faculty of Medicine, University of Granada, Granada 18071, Spain.
The functional significance of brain asymmetry is still largely unknown. Studying the level of correlation of neuropeptide-degrading activities between subcellular fractions such as synaptosomal, of the left and right hemispheres of male rats during development and aging could provide relevant data on their functional role during these periods. The present study analyzes the level of correlation of a enkephalin- or angiotensin III-degrading activity, such as membrane-bound arginyl-aminopeptidase activity (M-B ArgAP) between the left versus right homogenate and/or synaptosomal subcellular fractions obtained and processed independently from both brain hemispheres during development and aging.
View Article and Find Full Text PDFElectroredox N-Heterocyclic Carbene-Catalyzed Enantioselective (3 + 3) Annulation of Enals with 2-Naphthols.
Org Lett
December 2024
Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar, Punjab 140001, India.
Developing asymmetric transformations using electroredox and N-heterocyclic carbene (NHC)-catalyzed radical pathways is still desirable and challenging. Herein, we report an iodide-promoted β-carbon activation (LUMO-lowering process) of enals via electroredox carbene catalysis coupled with a hydrogen evolution reaction (HER). This strategy offers an environmentally friendly and sustainable route for rapidly assembling synthetically useful chiral naphthopyran-3-one in good to excellent yield and enantioselectivity using traceless electrons as inexpensive and greener oxidants.
View Article and Find Full Text PDFPhotoredox Radical Truce-Smiles Rearrangement of Sulfinyl Acrylamides with Bromodifluoroacetamides.
Org Lett
December 2024
Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan, Hunan 411105, China.
We herein report a photochemical Truce-Smiles rearrangement reaction of -sulfinyl acrylamides with bromodifluoroacetamides resulting in the synthesis of a series of aryl difluoroglutaramides in moderate to good yields. The asymmetric synthesis using chiral sulfinamides produced quaternary carboncentered glutaramide products with a modest enantioselectivity. This protocol effectively complements previous Truce-Smiles rearrangement methods involving -sulfonyl acrylamides.
View Article and Find Full Text PDFWant 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!