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Described here is an efficient protocol for intermolecular [2 + 2] cycloaddition of unactivated and unsymmetrical allenes and alkynes with unusual regioselectivity, counterintuitively favoring the most hindered isomer. CpRu(MeCN)PF served as a uniquely effective catalyst, providing diverse 3-alkylidenecyclobutenes with a broad scope and good functional group compatibility. Both experiments and DFT studies provided important insights into the mechanism, particularly the unusual regioselectivity.
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http://dx.doi.org/10.1021/jacs.5c11285 | DOI Listing |
J Am Chem Soc
September 2025
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.
Described here is an efficient protocol for intermolecular [2 + 2] cycloaddition of unactivated and unsymmetrical allenes and alkynes with unusual regioselectivity, counterintuitively favoring the most hindered isomer. CpRu(MeCN)PF served as a uniquely effective catalyst, providing diverse 3-alkylidenecyclobutenes with a broad scope and good functional group compatibility. Both experiments and DFT studies provided important insights into the mechanism, particularly the unusual regioselectivity.
View Article and Find Full Text PDFNat Chem
August 2025
Department of Chemistry, University of Wisconsin-Madison, Madison, WI, USA.
Azoles are important synthetic targets due to their diverse applications in areas ranging from human health to food security. Accordingly, access to N-functionalized azoles is an essential goal in modern synthetic chemistry. Surprisingly, however, the relied-upon azole N-alkylation strategies fundamentally limit the structural diversity of these important compounds that can be synthesized and studied.
View Article and Find Full Text PDFOrg Lett
August 2025
National Glycoengineering Research Center, Shandong Technology Innovation Center of Carbohydrate, Shandong University, Qingdao 266237, P. R. China.
Herein, we report that acyl fluorides enable the switchable selective acylation of vicinal 1,2--diol motifs in carbohydrates. While DMAP as a catalyst directs equatorial acylation, DBU highly promotes the thermodynamically unfavorable axial O-acylation, reversing conventional preferences. NMR studies and DFT calculations indicate that triple hydrogen bonding governs this unusual regioselectivity.
View Article and Find Full Text PDFNat Commun
July 2025
State Key Laboratory of Chemo and Biosensing, Advanced Catalytic Engineering Research Center of the Ministry of Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha, PR China.
Although ring-opening reactions of bicyclo[1.1.0]butanes (BCBs) provide a reliable platform for synthesizing functionalized cyclobutanes, current methods frequently encounter challenges such as poor diastereoselectivity, regioselectivity issues, and a lack of α- and β'-selective transformations.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Faculty of Chemistry and Food Chemistry, TU Dresden, Bergstrasse 66, 01069, Dresden, Germany.
The reductive activation of dichalcogenide probes by thiol-type oxidoreductases proceeds through a cascade of consecutive, partly reversible steps. Stereocontrol elements can modulate the reaction rates of these steps to reach substrate-controlled kinetic selectivity for reductase chemotypes in live cells. We now deploy regio-, diastereo-, template-, and pH-control elements to shape the reactivity of unprecedented bicyclic selenenyl sulfides (SeSP), arriving at probes that selectively target the mammalian selenoenzyme thioredoxin reductase TrxR1.
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