6575-25-3Relevant articles and documents
Three-coordinate copper(II) alkynyl complex in C-C bond formation: The sesquicentennial of the glaser coupling
Warren, Timothy H.,Bakhoda, Abolghasem,Okoromoba, Otome E.,Greene, Christine,Boroujeni, Mahdi Raghibi,Bertke, Jeffery A.
supporting information, p. 18483 - 18490 (2020/11/27)
Copper(II) alkynyl species are proposed as key intermediates in numerous Cu-catalyzed C-C coupling reactions. Supported by a β-diketiminate ligand, the three-coordinate copper(II) alkynyl [CuII]-C≡CAr (Ar = 2,6-Cl2C6H3) forms upon reaction of the alkyne H-C≡CAr with the copper(II) tertbutoxide complex [CuII]-OtBu. In solution, this [CuII]-C≡CAr species cleanly transforms to the Glaser coupling product ArC≡C-C≡CAr and [CuI](solvent). Addition of nucleophiles R′C≡C-Li (R′ = aryl, silyl) and Ph-Li to [CuII]-C≡CAr affords the corresponding Csp-Csp and Csp-Csp2 coupled products RC≡C-C≡CAr and Ph-C≡CAr with concomitant generation of [CuI](solvent) and {[CuI]-C≡CAr}-, respectively. Supported by density functional theory (DFT) calculations, redox disproportionation forms [CuIII](C≡CAr)(R) species that reductively eliminate R-C≡CAr products. [CuII]-C≡CAr also captures the trityl radical Ph3C· to give Ph3C-C≡CAr. Radical capture represents the key Csp-Csp3 bond-forming step in the copper-catalyzed C-H functionalization of benzylic substrates R-H with alkynes H-C≡CR′ (R′ = (hetero)aryl, silyl) that provide Csp-Csp3 coupled products R-C≡CR via radical relay with tBuOOtBu as oxidant.
HORMONE RECEPTOR MODULATORS FOR TREATING METABOLIC MUTAGENIC AND FIBROTIC CONDITIONS AND DISORDERS
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Page/Page column 200-201, (2019/04/11)
The invention relates to activators of FXR useful in the treatment of autoimmune disorders, liver disease, intestinal disease, kidney disease, cancer, and other diseases in which FXR plays a role, having the Formula (I): wherein L1, A, X1
The Dual Role of 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) in the Synthesis of Terminal Aryl- and Styryl-Acetylenes via Umpolung Reactivity
Morri, Ashok Kumar,Thummala, Yadagiri,Doddi, Venkata Ramana
supporting information, p. 4640 - 4643 (2015/09/28)
The dual role of the bicyclic amidine base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was demonstrated in a synthesis of terminal aryl- and styryl-acetylenes. Mechanistically, a tandem process involving elimination/Umpolung/protonation occurs in a single step to generate terminal aryl- and styryl-acetylenes from geminal dibromoalkenes. The key to the success of this transformation lies in the organobase-mediated generation of the acetylide from the 1-bromoalkynes at room temperature. The unique characteristics of DBU as an inherently safer reagent make it an attractive alternative to previous systems wherein required pyrophoric reagents and nonambient temperatures remain unsolved issues. The procedure does not work for the synthesis of alkyl-acetylenes.