Electrocarboxylation of Carbon Dioxide with Polycyclic Aromatic Hydrocarbons Using Ni as the Cathode

Abstract

Using Ni cathode and Al sacrificial anode, the electrocarboxylation of polycyclic aromatic hydrocarbons (naphthalene, 5-methylnaphthalene, anthracene, phenanthrene and 1H-indene) with carbon dioxide (4 MPa) could be successfully performed in an undivided cell containing n-Bu 4 NBr-DMF supporting electrolyte with a constant current at room temperature, affording the corresponding trans-dicarboxylic acids in good to excellent yields (62%-90%). Among the examined cathode materials (Ni, Pt, Ag, Cu and Zn), Ni and Pt cathodes exhibited a good catalytic activity for the electrocarboxylations. In addition, the experimental results indicated that electrolytic conditions (conducting salts, electricity, CO 2 pressure and temperature) could also affect the result of the electrocarboxylation. According to the results of the electrocarboxylations and CV (cyclic voltammetry), a possible electrochemical reaction mechanism was also proposed.

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

“…804 Yuan and co-workers reported a method to achieve dearomative carboxylation of polycyclic aromatic compounds such as naphthalene and anthracene (Figure 46E). 805 Arene and CO 2 likely undergo reductions simultaneously. The ensuing CO 2 radical anion can react with arenes; likewise, arene radical anions can engage CO 2 .…”

Transition Metal‐Free CO2 Fixation into New Carbon–Carbon Bonds

“…a) EC of ethyl cinnamate reported by Lu and co-workers. [44] ChemSusChem 2018, 11,3056 -3070 www.chemsuschem.org means of EC. [43] Scheme23.…”

“…In 2010 Yuan and co-workers [44] reportedt he EC of polycyclic aromatic hydrocarbons 105 at high pressures of CO 2 ,a ffording different cyclic and polycyclic 1,4-dicarboxylic acids 106 in moderate to excellent yields (55-92 %; Scheme 25). Mechanistic studies revealed that the reduction of CO 2 andthe polyaromatics occurs at the same potential, and therefore the radical anions of both species coexist in the reaction medium.…”

“…EC of polycyclic aromatic hydrocarbons developedb yY uan and co-workers. [44] ChemSusChem 2018, 11,3056 -3070 www.chemsuschem.org means of EC. Te rminal alkynes 114 react with CO 2 at the terminal position maintaining intact the triple bond.S pecifically, DuÇach and co-workers reported in 2001 the first EC of terminal alkynes affording as eries of 2-ynoic acid derivatives 115 in good to excellent yields (70-95 %; Scheme26b).…”

Spirocyclizative Remote Arylcarboxylation of Non-Activated Arenes with CO2 via Visible-Light-Induced Reductive Dearomatization

“…In contrast, only limited important advances have been made in the dearomatization of electronically unbiased aromatics such as naphthalene and benzene derivatives that possess high resonance stabilization energy. 6,[25][26][27][28][29][30][31][32][33][34] Of particular note, the You group recently reported an elegant highly diastereoselective 1,4-difunctionalization of 1-naphthamides via Palladium-catalyzed dearomatization at slightly elevated temperature. 25 Therefore, the dearomatization of non-activated arenes remains challenging, and the development of a mild and complementary protocol for dearomatization of non-activated arenes is highly desirable.…”