Acid‐Promoted Expeditious Syntheses of Aminated Dibenzosultams via Palladium/Norbornene Cooperatively Catalysed C−H Amination/Arylation

Abstract

Herein we reported a protocol to access aminated benzofused sultams through sequential ortho‐amination, followed by ipso‐arylation of aryl iodide bearing sulfonamide functional group via palladium/norbornene coorperative catalysis. This reaction has showcased a broad spectrum of substrate scope under mild conditions with moderate to good efficiency.

Regioselective oxidative cleavage of conjugated dienes to access α,β-unsaturated nitriles

“…After investigating the substrate scope, we decided to use our method for the synthesis of N-15 labelled cinnamonitrile 2* . After evaluating all commercially available N-15 labelled ammonium salts, we found that N-15 ammonium chloride 6 ( 15 NH 4 Cl; $169 per 1 g) and N-15 ammonium acetate 15 ( 15 NH 4 OAc; $491 per g) were the most favourable options, with cost considerations leading us to choose 15 NH 4 Cl. Extra base was essential in the current transformation with NH 4 Cl (see the ESI, page 20, Scheme S4-1†).…”

Palladium-Catalyzed C–H Amination/[2 + 3] or [2 + 4] Cyclization via C(sp3 or sp2)–H Activation

“…Based on the mechanism research of the above documents, , as well as our experimental results and DFT calculations, we propose a reasonable mechanism. First, o -iodotoluene and Pd(0) undergo oxidative addition to generate intermediate I , which is followed by insertion into norbornadiene and subsequent ortho -C–H activation.…”

“…Subsequently, the strategy was further extended to the construction of allene-and sulfur-containing skeleton. 10…”

“…In 2020, we further verified the carboxylic acid exchange process by using control experiments. Subsequently, the strategy was further extended to the construction of allene- and sulfur-containing skeleton . Through the two-component tandem reaction reported above, we attempted the unreported three-component C­(sp 3 )–H activation tandem reaction to solve the problem of o -methyl activation (Scheme c).…”

Enantioselective Assembly of Ferrocenes with Axial and Planar Chiralities via Palladium/Chiral Norbornene Cooperative Catalysis

“…A set of control experiments were subsequently conducted to understand the role of each component. The pivalate anion proved critical for this reaction, − as the yield of 3a decreased dramatically either without pivalic acid or using Pd­(OAc) 2 instead of Pd­(OPiv) 2 as the catalyst (entries 2–3). Changing the cocatalyst N 1 * to 2-amide-substituted norbornene N 2 * led to no 3a formation, with large amounts of starting materials remaining, indicative of the importance of the ester group in N 1 * (entry 4).…”