By combining catalytic nucleophilic enamine activation with Pd-catalyzed C-H activation of allylarenes, the first oxidative allylic alkylation of unactivated ketones was achieved. Mechanistically, the Pd-catalyzed allylic C-H activation and proline-catalyzed ketone nucleophilic activation worked synergistically for the oxidative cross-coupling between allylarenes and unactivated ketones.
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http://dx.doi.org/10.1021/ol501584d | DOI Listing |
J Am Chem Soc
January 2025
The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
Ni-catalyzed asymmetric reductive cross-coupling reactions provide rapid and modular access to enantioenriched building blocks from simple electrophile precursors. Reductive coupling reactions that can diverge through a common organometallic intermediate to two distinct families of enantioenriched products are particularly versatile but underdeveloped. Here, we describe the development of a bis(oxazoline) ligand that enables the desymmetrization of -anhydrides.
View Article and Find Full Text PDFOrg Lett
January 2025
School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Thiruvananthapuram 695551, Kerala, India.
Herein, we report a formal C-C bond azidation and cyanation of unactivated aliphatic ketones using commercially available tosyl azide and cyanide, respectively. A visible-light-mediated organophotocatalyst enables radical azidation and cyanation of ketone-derived pro-aromatic dihydroquinazolinones (under mostly redox-neutral conditions) as supported by preliminary mechanistic studies. These metal-free and scalable protocols can be used to synthesize tertiary, secondary, and primary alkyl azides and nitriles with good functional group tolerance and postsynthetic diversification of the azide group, including bioconjugation.
View Article and Find Full Text PDFJ Org Chem
December 2024
Department of Chemistry, Shanghai University, 99 Shangda Road, Shanghai 200444, China.
The first deoxygenative hydrosilylation of ketones promoted by samarium diiodide and samarium has been reported. In this approach, secondary alkyl silanes are synthesized from unactivated ketones and chlorosilanes in one step. The carbonyl group of ketones is activated by SmI-mediated single-electron transfer process, which follows a deoxygenative elimination of O=Sm.
View Article and Find Full Text PDFStructurally constraining p-block elements has become a powerful strategy for bond activation chemistry with main group compounds. Traditionally, this approach focuses on mononuclear centers, yet applying structural constraints to systems with element-element bonds remains underexplored. In this study, we introduce a cation featuring a structural constraint-elongated P-P bond that spontaneously adds to unactivated alkynes, alkenes, aldehydes, and ketones.
View Article and Find Full Text PDFOrg Lett
November 2024
Key Laboratory of Chinese Medicinal Resource from Lingnan, Ministry of Education, School of Pharmaceutical Sciences, Guangzhou University of Chinese Medicine, Guangzhou 510006, China.
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