Rhodium‐katalysierte oxidative Olefinierung von C‐H‐Bindungen in Acetophenonen und Benzamiden

Palladium‐Catalyzed and Hybrid Acids‐Assisted Synthesis of [60]Fulleroazepines in One Pot under Mild Conditions: Annulation of N‐Sulfonyl‐2‐aminobiaryls with [60]Fullerene through Sequential C‐H Bond Activation, C‐C and C‐N Bond Formation

“…of pTsOH in 6.2 mL of ODCB/TFA (6:0.2) at ambient temperature, the desired monofunctionalized fullerene product 2a was isolated in good chemical yield (37%; 48% based on converted C 60 , entry 9). K 2 S 2 O 8 was also an effective oxidant for this functionalization when compared to other metal oxidizing agents (entry 10 vs. entries [4][5][6][7][8]. We noted that increasing reaction temperature or time did not improve reaction yields (entries [11][12][13][14][15].…”

“…A number of directing groups such as carbonyl-based, nitrogen-containing groups or an allyl moiety have been utilized. [6] We noticed that the utility of 2-aminobiaryls to construct different sizable heterocycles has also been developed; [7] for example, Miura et al reported the cross-coupling of Nsulfonyl-2-aminobiaryls with alkenes to afford phenanthridine derivatives [8] (six-membered rings). In 2005, Buchwald and co-workers demonstrated a highly efficient Pd(II)-catalyzed C À H bond activation/intramolecular amidation for the synthesis of carbazoles [9] (five-membered rings) from 2-acetaminobiphenyls.…”

Access to Sultams by Rhodium(III)‐Catalyzed Directed CH Activation

“…[9] In this context, rhodium(III)-catalyzed reactions [10] using a wide range of carbonyl-derived directing groups such as benzamides, [11] acetanilides, [12] imines, [13] ketones, [14] and carboxylic acids [15] were reported, thus illustrating the utility of this reactivity concept. Despite their critical importance, aryl sulfonamides have, to the best of our knowledge, not been explored with rhodium catalysts.…”

Oxidative Alkenylation/Annulation of Benzimidates via Ruthenium(II)‐Catalyzed CH Activation to Generate 3‐Methyleneisoindolin‐1‐ones

“…(8) tion relative to the ester carbonyl group, raising the possibility of rapid H/D exchange on the NH-acidic imidate group before subsequent intramolecular addition. Based on our mechanistic studies and the literature data, [1,2,19] a plausible mechanism for this oxidative alkenylation/annulation cascade reaction is proposed (Scheme 3). Initially, a reversible C À H metalation of the ruthenium(II) complex and 1 produces the fivemembered ruthenacycle A, followed by insertion with alkene to give the intermediate B.…”

“…(1)]. [19,20] In 2013, Li developed an Rh(III)-catalyzed annulation of aryl ketone O-methyl oximes and isocyanates to generate Scheme 1. Methods for synthesizing 3-methyleneisoindolin-1-ones based on C À H activation.…”