Electro-Oxidative C–C Alkenylation by Rhodium(III) Catalysis

Abstract

Experimental procedures and compound characterization data, including the 1 H/ 13 C NMR spectra (PDF)

Making electrochemistry easily accessible to the synthetic chemist

“…The advantages of the setup employed will be discussed for each type of reaction. See the following reviews for specific transformations: cross coupling, [24][25][26] CH activation, [27][28][29][30][31][32][33][34][35][36] asymmetric synthesis, 14 heterocycle formation, [37][38][39] arylation, 40 fluorination, 41 organometallic catalysis, 42,43 cation pool method. 44 The different types of reactions can be summarised as: (1) direct electrochemical reaction with solvent degradation as counter reaction, (2) direct electrochemical reaction with nonsolvent degradation as counter reaction, (3) mediated or catalysed electrochemical reaction, (4) redox combined electrochemical reaction (Fig.…”

“…In this case, the active species of the electrocatalyst is formed and/or turned over by electricity. 28,30,[32][33][34] This concept has also been applied to photocatalysts. 121 Morrill and co-workers have developed the electrocatalysed deconstructive chlorination of cycloalkanols (Scheme 6).…”

“…This tutorial review provides an introduction to electrochemistry and is not designed to be an extensive review of all synthetic electrochemical examples. For further information recent reviews and the references therein are recommended: certain transformations including cross coupling, [24][25][26] CH activation, [27][28][29][30][31][32][33][34][35][36] asymmetric synthesis, 14 heterocycle formation, [37][38][39] arylation, 40 fluorination, 41 organometallic catalysis, 42,43 cation pool method, 44 continuous reactor types, [45][46][47][48][49][50][51][52][53][54][55] analytical tools 56,57 and general reviews and perspectives. [1][2][3][4][5][6][7][8][9][10][11][12][13]…”

Synthesis of thioethers, arenes and arylated benzoxazoles by transformation of the C(aryl)–C bond of aryl alcohols

“…30 Their direct activation and functionalization are kinetically inert. In this regard, very limited research advances have been achieved by far and wide application of developed methods is oen hindered, owing to the requirement of indispensable directing group modied substrates, [31][32][33][34] highly toxic reagents and strong oxidants. 30,35 The development of a versatile and robust strategy for the activation and functionalization of C(aryl)-C bonds that allows aryl alcohols to be used as latent arylating agents is highly desirable, but very challenging.…”

Rhodaelectrocatalysis for Annulative C−H Activation: Polycyclic Aromatic Hydrocarbons through Versatile Double Electrocatalysis

“…[7,8] Significant recent impetus was gained by the merger of electrocatalysis with organometallic C À Ha ctivation, thus avoiding the use of toxic and expensive metal oxidants. [9,10] While electrochemical polymerization has been exploited for the synthesis of conducting materials, [11] the bottom-up assembly of atomically precise PA Hm otifs by electrooxidative catalysis has thus far unfortunately proven elusive.I n sharp contrast, we have now devised an ovel strategy for merging two distinct electrocatalytic transformations for the chemoselective assembly of decorated PA Hs.T he development of an unprecedented rhodaelectrocatalyzed [12] C À H activation for the annulative [13] [2+ +2+ +2] cycloaddition of userfriendly boronic acids set the stage for an electro-catalyzed dehydrogenation in ar esource-economical manner ( Figure 1). Salient features of our method include 1) rapid, modular access to PA Hs through double electrocatalysis, 2) electricity as as ustainable oxidant, 3) the formation of six new C À Cb onds in ap rogrammable fashion, and 4) outstanding levels of chemoselectivity through metallaelectrocatalysis.…”