125617-18-7Relevant articles and documents
A 3,4-dimercapto-3-cyclobutene-1,2-dione-chelated ruthenium carbene catalyst for: Z -stereoretentive/stereoselective olefin metathesis
Wang, Tao,Xie, Qingxiao,Guo, Weijie,Wu, Shutao,Zhang, Huiqing,Wang, Jianhui,Wu, Botao
, p. 6473 - 6483 (2019)
A ruthenium carbene catalyst chelated with a 3,4-dioxocyclobut-1-ene-1,2-dithiolate ligand was synthesized and its molecular structure was determined by single-crystal X-ray diffraction. The Ru catalyst had excellent catalytic activity with high yields and good Z/E ratios for the ring opening metathesis polymerization (ROMP) of norbornene (yield: 96%/Z/E: 86 : 14) and 1,5-cyclooctadiene (yield: 86%/Z/E: 91 : 9) and for ring opening cross metathesis (ROCM) reactions of norbornene/5-norbornene-2-exo, 3-exo-dimethanol with styrene (yields: 64%-92%/Z/E: 97 : 3-98 : 2) or 4-fluorostyrene (yield: 46%-94%/Z/E: 98 : 2). The catalyst also had high Z-stereoretentivity (91 : 9-98 : 2) for cross-metathesis (CM) reactions of terminal olefins with (Z)-2-butene-1,4-diol. More importantly, the catalyst had moderate Z-stereoselectivity for homometathesis reactions of terminal olefins giving cis-olefins as the major products (Z/E ratios of 70 : 30-77 : 23). Like other Ru carbene complexes, the catalyst tolerates many different functional groups. The presented data, supported by DFT calculations, show that our catalyst, bearing a chelating 3,4-dioxocyclobut-1-ene-1,2-dithiolate ligand, exhibits higher stability towards air than Hoveyda's stereoretentive complex systems.
Photocatalyzed Diastereoselective Isomerization of Cinnamyl Chlorides to Cyclopropanes
Dykstra, Ryan,Gutierrez, Osvaldo,Martin, Robert T.,Tambar, Uttam K.,Troian-Gautier, Ludovic,Xu, Bin
, p. 6206 - 6215 (2020/04/27)
Endergonic isomerizations are thermodynamically unfavored processes that are difficult to realize under thermal conditions. We report a photocatalytic and diastereoselective isomerization of acyclic cinnamyl chlorides to strained cyclopropanes. Quantum mechanical calculations (uM06-2X and DLPNO), including TD-DFT calculations, and experimental studies provide evidence for the energy transfer from an iridium photocatalyst to the allylic chloride substrate followed by C-Cl homolytic cleavage. Subsequent Cla￠ radical migration forms a localized triplet 1,3-diradical intermediate that, after intersystem crossing, undergoes ring-closing to form the desired product. The mild reaction conditions are compatible with a broad range of functional groups to generate chlorocyclopropanes in high yields and diastereoselectivities. A more efficient process is developed by addition of a catalytic amount of a nickel complex, and we propose a novel role for this cocatalyst to recycle an allyl chloride byproduct generated in the course of the reaction. The reaction is also shown to be stereoconvergent, as an E/Z mixture of cinnamyl chlorides furnish the anti-chlorocyclopropane product in high diastereoselectivity. We anticipate that the use of a visible light activated photocatalyst to transform substrates in combination with a transition metal catalyst to recycle byproducts back into the catalytic cycle will provide unique opportunities for the discovery of new reactivity.
Palladium-catalyzed allylic C-H oxidation under simple operation and mild conditions
Guo, Yunlong,Shen, Zengming
supporting information, p. 3103 - 3107 (2019/03/26)
We discovered an effective and simple system (Pd/BQ/air/r.t.) for making allylic alcohols through Pd-catalyzed allylic C-H bond functionalization. This approach exhibits advantages due to its simple operation, mild conditions, and environmentally benign features. By modifying reaction conditions, it can be suitable for preparing unsaturated aldehydes, allylic esters, ethers, and amines.
