The dual Lewis acid/base catalytic system, generated from N-methylimidazole (NMI), (R)-1,1'-bi-2-naphthol [(R)-BINOL], and Ti(OiPr)4, effectively catalyzes the enantioselective alkynylation of aldehydes in the presence of Et2Zn in good yields and excellent enantioselectivities of up to 94% ee at room temperature. The mild reaction conditions make it possible to use functional alkynes in this asymmetric addition.
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http://dx.doi.org/10.1021/jo0707535 | DOI Listing |
Org Lett
January 2025
Key Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou 350108, China.
Alternating current electrolysis has emerged as a promising technique for addressing challenging redox reactions that are otherwise difficult or impossible for direct current electrolysis. Under mild and transition-metal-free reaction conditions, a general electrochemical denitrative cyclization of nitroarenes was developed to access various cyclic sulfone-containing derivatives of biological significance. The key to success lies in the facile manipulation of multiple redox events upon rapid alternating polarity switching to enhance the selectivity and efficiency.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St Andrews KY16 9ST, U.K.
New approaches to achieve facile and reversible dihydrogen activation are of importance for synthesis, catalysis, and hydrogen storage. Here we show that low-coordinate magnesium oxide complexes [{(nacnac)Mg}(μ-O)] , with nacnac = HC(RCNDip), Dip = 2,6-PrCH, R = Me (), Et (), Pr (), readily react with dihydrogen under mild conditions to afford mixed hydride-hydroxide complexes [{(nacnac)Mg}(μ-H)(μ-OH)] . Dehydrogenation of complexes is strongly dependent on remote ligand substitution and can be achieved by simple vacuum-degassing of (R = Pr) to regain .
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Key Laboratory for Green Organic Synthesis and Application of Hunan Province, Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan 411105, China.
Herein, we report a cascade annulation of readily available isocyanobiaryls with simple aldehydes photoredox catalysis, providing a straightforward approach towards valuable 6-hydroxyalkylated phenanthridines. Mechanistic studies indicated the generation of a key acyl radical from aldehydes by hydrogen atom abstraction with a bromine radical. This protocol exhibits exceptional chemoselectivity, excellent tolerance of various functional groups and mild reaction conditions.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872, United States.
Enthalpy is often the focal point when designing monomers for polymer circularity, but much less is explored on how entropy can be exploited to create polymers with synergistic circularity and properties. Here, we design a series of spiro-lactones (SLs) with closed-chain cycloalk(en)yl substituents at the α,α-position of δ-valerolactone (δVL), which, when combined with the parent δVL and -α,α-dialkyl-substituted δVL with open-chain alkyl groups, provide a desired platform for exploring the circular polymer design by focusing on the entropy change of polymerization. These SLs exhibit finely balanced (de)polymerizability that is regulated chiefly by entropy differentiation, allowing both the facile synthesis of polyester PSLs ( up to 1000 kg mol) in a living fashion and selective depolymerization of the PSLs to completely recover monomers under mild conditions (using a recyclable catalyst at 100 °C).
View Article and Find Full Text PDFNat Commun
January 2025
Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai, 200240, China.
In drug development, the substitution of benzene rings in aniline-based drug candidates with saturated bridged bicyclic ring systems often enhances pharmacokinetic properties while preserving biological activity. However, current efforts predominantly focuses on bicyclo[1.1.
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