729-17-9Relevant articles and documents
Bathocuproine-Enabled Nickel-Catalyzed Selective Ullmann Cross-Coupling of Two sp 2-Hybridized Organohalides
Li, Yuqiang,Yin, Guoyin
supporting information, p. 1657 - 1661 (2021/09/13)
Cross-coupling reactions are essential for the synthesis of complex organic molecules. Here, we report a nickel-catalyzed Ullmann cross-coupling of two sp 2-hybridized organohalides, featuring high cross-selectivity when the two coupling partners are used in a 1:1 ratio. The high chemoselectivity is governed by the bathocuproine ligand. Moreover, the mild reductive reaction conditions allow that a wide range of functional groups are compatible in this Ullmann cross-coupling.
para-Selective arylation and alkenylation of monosubstituted arenes using thianthreneS-oxide as a transient mediator
Chen, Xiao-Yue,Nie, Xiao-Xue,Wu, Yichen,Wang, Peng
supporting information, p. 5058 - 5061 (2020/05/18)
Using thianthreneS-oxide (TTSO) as a transient mediator,para-arylation and alkenylation of mono-substituted arenes have been demonstratedviaapara-selective thianthrenation/Pd-catalyzed thio-Suzuki-Miyaura coupling sequence under mild conditions. This reaction features a broad substrate scope, and functional group and heterocycle tolerance. The versatility of this approach was further demonstrated by late-stage functionalization of complex bioactive scaffolds, and direct synthesis of some pharmaceuticals, including Tetriprofen, Ibuprofen, Bifonazole, and LJ570.
Base-free nickel-catalysed decarbonylative Suzuki–Miyaura coupling of acid fluorides
Malapit, Christian A.,Bour, James R.,Brigham, Conor E.,Sanford, Melanie S.
, p. 100 - 104 (2018/11/25)
The Suzuki–Miyaura cross-coupling of organoboron nucleophiles with aryl halide electrophiles is one of the most widely used carbon–carbon bond-forming reactions in organic and medicinal chemistry1,2. A key challenge associated with these transformations is that they generally require the addition of an exogenous base, the role of which is to enable transmetallation between the organoboron nucleophile and the metal catalyst3. This requirement limits the substrate scope of the reaction because the added base promotes competitive decomposition of many organoboron substrates3–5. As such, considerable research has focused on strategies for mitigating base-mediated side reactions6–12. Previous efforts have primarily focused either on designing strategically masked organoboron reagents (to slow base-mediated decomposition)6–8 or on developing highly active palladium precatalysts (to accelerate cross-coupling relative to base-mediated decomposition pathways)10–12. An attractive alternative approach involves identifying combinations of catalyst and electrophile that enable Suzuki–Miyaura-type reactions to proceed without an exogenous base12–14. Here we use this approach to develop a nickel-catalysed coupling of aryl boronic acids with acid fluorides15–17, which are formed in situ from readily available carboxylic acids18–22. This combination of catalyst and electrophile enables a mechanistic manifold in which a ‘transmetallation-active’ aryl nickel fluoride intermediate is generated directly in the catalytic cycle13,16. As such, this transformation does not require an exogenous base and is applicable to a wide range of base-sensitive boronic acids and biologically active carboxylic acids.
