Pd(OAc)₂/o-Chloranil/M(OTf)_n: A Catalyst for the Direct C–H Arylation of Polycyclic Aromatic Hydrocarbons with Boryl-, Silyl-, and Unfunctionalized Arenes

Abstract

Pd(OAc)(2)/o-chloranil/M(OTf)(n) can effectively promote the C-H arylation of fluoranthene with arylboron compounds or arylsilanes. The reaction takes place with high regioselectivity at the C3 position of fluoranthene. Moreover, the new catalytic system allows the use of unfunctionalized arenes as coupling partners in the arylation of polycyclic aromatic hydrocarbons.

One-shot K-region-selective annulative π-extension for nanographene synthesis and functionalization

“…Our APEX campaign 29 30 31 32 33 34 began when we serendipitously discovered Pd(OAc) 2 / o -chloranil as the first-generation C–H activation catalyst for PAHs in 2011 (ref. 35 ).…”

Palladium/Copper Dual Catalysis for the Cross‐Coupling of Aryl(trialkyl)silanes with Aryl Bromides

“…Moreover, aryl(triethyl)silanes are easily prepared by catalytic C−H silylation of aromatic hydrocarbons . However, aside from a few exceptions, such silanes do not participate in cross‐couplings. Consequently, they are often converted into aryl halides, boronic acids, or stannanes (Figure , top) before the coupling reaction .…”

“…[1,2] Among awide variety of organometallic nucleophiles,s imple organo-(trialkyl)silanes have ideal properties in terms of their stability,h igh solubility in various organic solvents,l ow toxicity,e asy handling, and high accessibility.M oreover, aryl(triethyl)silanes are easily prepared by catalytic CÀH silylation of aromatic hydrocarbons. [3] However,a side from af ew exceptions, [4][5][6][7] such silanes do not participate in crosscouplings.C onsequently,t hey are often converted into aryl halides,boronic acids,orstannanes (Figure 1, top) before the coupling reaction. [8] Accordingly,t hese additional transformations reduce the merit of silicon reagents.…”

Biaryl Synthesis through Metal‐Catalyzed C–H Arylation

“…Following their methods, various fluorobiphenyls such as 147, which are important motifs for pharmaceuticals and organic materials, can be produced. In 2012, Itami [212] developed a novel palladium catalytic system for the C-H/C-H cross-coupling of PAHs and simple arenes. Treatment of fluoranthene (148) with excess mesitylene at 50 • C under the influence of Pd(OAc) 2 /o-chloranil/AgOTf afforded 3-mesitylfluoranthene (149) in 74% yield with virtually complete regioselectivity (C3 position) (Scheme 17.43).…”