The selective δ-C(sp )-H acetoxylation of N-(SO Py)-protected amino acid derivatives has been accomplished by using palladium-catalysis and PhI(OAc) (PIDA) as both terminal oxidant and acetoxy source. The distinct structural and electronic features of the SO Py compared to more traditional carbonyl-based directing groups is essential to override the otherwise more favourable competitive intramolecular C-H amination. The δ-site selectivity predominates over traditionally more favorable 5-membered cyclopalladation at competitive γ-CH . Experimental and DFT mechanistic studies provide important insights about the mechanism and the underlying factors controlling the chemo- and regioselectivity.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC9828559 | PMC |
| http://dx.doi.org/10.1002/anie.202209865 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Palladium-Catalyzed Acetoxylation of γ-Dehydro-aryl-himachalene: The Synthesis of a Novel Allylic Acetoxylated Sesquiterpene and a π-Allyl Palladium(II) Complex.
Molecules
October 2024
Laboratory of Molecular Chemistry, Faculty of Sciences Semlalia, Cadi Ayyad University, B.P. 2390, Marrakech 40001, Morocco.
Allylic oxygenated derivatives of himachalenes are highly valued molecules due to their potential applications in perfumery, cosmetics, and pharmaceuticals. Previous attempts at catalyzed allylic oxidation of himachalenes led to the formation of a very stable η-allyl palladium complex, preventing any further reaction development. Herein, we present the first successful palladium-catalyzed synthesis of a novel allylic acetoxylated derivative of himachalenes.
View Article and Find Full Text PDFTotal synthesis of (-)-cylindrocyclophane A facilitated by C-H functionalization.
Science
November 2024
Department of Chemistry, Emory University, Atlanta, GA 30322, USA.
(-)-Cylindrocyclophane A is a 22-membered C-symmetric [7.7]paracyclophane that bears bis-resorcinol functionality and six stereocenters. We report a synthetic strategy for (-)-cylindrocyclophane A that uses 10 C-H functionalization reactions, resulting in a streamlined route with high enantioselectivity and efficiency (17 steps).
View Article and Find Full Text PDFFluorescent, pH, and UCST Responsive Polymer Nanomaterials for Treatment of Recurrent Miscarriage.
J Fluoresc
September 2024
Reproductive Medicine Center, The First Affiliated Hospital of Soochow University, Suzhou, Jiangsu, China.
Recurrent miscarriage (RM), defined as three or more consecutive spontaneous miscarriages, affects many women of childbearing age. The pathological basis of RM is an imbalance in apoptosis, with the MDM2-p53 pathway playing a crucial role. In this study, we synthesized poly(6-acetoxyl-ε-caprolactone)-graft-(4-amino-benzimidazole) (PCCL-4-ABI) by modifying poly(6-acetoxyl-ε-caprolactone) (PCCL) with 4-amino-benzimidazole (4-ABI).
View Article and Find Full Text PDFPalladium-catalyzed electrochemical C(sp)-H acetoxylation of alcohol derivatives with an -directing group.
Org Biomol Chem
September 2024
Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
Palladium-catalyzed electrochemical C(sp)-H acetoxylation to prepare 1,2-diol derivatives was achieved using oxime ethers as -directing groups. Various substrates containing alkoxy groups with a methyl branch at the α-position as well as norbornan-2-ol derivative were acetoxylated only using a catalytic amount of Pd(OAc) along with NaOAc/AcO/AcOH under anodic oxidation conditions.
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!