Cyclization of propargylic alcohols with CO is an important reaction in industry, and noble-metal catalysts are often employed to ensure the high product yields under environmentally friendly conditions. Herein a porous noble-metal-free framework 1 with large 1D channels of 1.66 nm diameter was synthesized for this reaction. Compound 1 exhibits excellent acid/base stability, and is even stable in corrosive triethylamine for one month. Catalytic studies indicate that 1 is an effective catalyst for the cyclization of propargylic alcohols and CO without any solvents under mild conditions, and the turnover number (TON) can reach to a record value of 14 400. Furthermore, this MOF catalyst also has rarely seen catalytic activity when the biological macromolecule ethisterone was used as a substrate. Mechanistic studies reveal that the synergistic catalytic effect between Cu and In plays a key role in the conversion of CO .
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http://dx.doi.org/10.1002/anie.201811506 | DOI Listing |
Int J Mol Sci
December 2024
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China.
α-Hydroxy ketones are a crucial class of organic compounds prevalent in natural products and pharmaceutical molecules. The CO-promoted hydration of propargylic alcohols is an efficient method for the synthesis of α-hydroxy ketones. Herein, an ionic liquid (IL) was designed to catalyze this reaction individually under atmospheric CO pressure, volatile organic solvents, and additives.
View Article and Find Full Text PDFOrg Lett
January 2025
Materials Tech Laboratory for Hydrogen & Energy Storage, Ningbo Institute of Materials Technology and Engineering (NIMTE), Chinese Academy of Sciences, Ningbo 315201, P. R. China.
A new sequential deprotonation strategy of dimethyl sulfoxide (DMSO) and propargyl alcohol in the presence of a base was developed for the generation of the α-hydroxyl carbanion, which enables rapid and controllable access to a wide range of valuable highly functionalized furans in one pot from alkynes and aldehydes under transition-metal- and additive-free conditions. Preliminary mechanistic studies revealed the crucial role of the base and DMSO. More importantly, deuterium labeling experiments confirmed the formation of the α-hydroxyl carbanion.
View Article and Find Full Text PDFOrg Lett
January 2025
Research Center for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University, 220 Handan Lu, Shanghai 200433, People's Republic of China.
An efficient dehydrative coupling of propargylic alcohols with diarylphosphine oxides to construct tetrasubstituted allenylphosphoryl compounds in the presence of a Pd/Brønsted acid co-catalyst has been developed. As a benefit from the use of a Brønsted acid, this reaction could perform under mild conditions with excellent yields, accommodating a wide range of functional groups. The potential utility of this method has also been demonstrated.
View Article and Find Full Text PDFOrg Biomol Chem
December 2024
National and Local Joint Engineering Research Center of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China.
Deoxyfluorination is one of the most practical methods for introducing fluorine atoms, since hydroxyl groups are commonly found in organic small molecules. Traditional fluorination methods often rely on hazardous fluorinating reagents. Herein, we report the deoxyfluorination of propargyl alcohols using sulfur hexafluoride (SF) as a safe fluorinating agent under photocatalytic conditions.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, Tianjin 300071, China.
The direct enantioselective functionalization of C(sp)-H bonds in organic molecules could fundamentally transform the synthesis of chiral molecules. In particular, the enantioselective oxidation of these bonds would dramatically change the production methods of chiral alcohols and esters, which are prevalent in natural products, pharmaceuticals, and fine chemicals. Remarkable advances have been made in the enantioselective construction of carbon-carbon and carbon-nitrogen bonds through the C(sp)-H bond functionalization.
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