A unified and modular approach to the teleocidin B family of natural products is presented that proceeds in 11 steps and features an array of interesting strategies and methods. Indolactam V, the known biosynthetic precursor to this family, was accessed through electrochemical amination, Cumediated aziridine opening, and a remarkable base-induced macrolactamization. Guided by a desire to minimize concession steps, the tactical combination of C-H borylation and a Sigman-Heck transform enabled the convergent, stereo-controlled synthesis of the teleocidins.

Herein, we describe a new catalytic approach to accessing aromatic amines from an abundant feedstock, namely phenols. The most reliable catalytic method for converting phenols to aromatic amines uses an activating group, such as a trifluoromethane sulfonyl group. However, this activating group is eliminated as a leaving group during the amination process, resulting in significant waste. Our nickel-catalyzed decarboxylation reaction of aryl carbamates forms aromatic amines with carbon dioxide as the only byproduct. As this amination proceeds in the absence of free amines, a range of functionalities, including a formyl group, are compatible. A bisphosphine ligand immobilized on a polystyrene support (PS-DPPBz) is key to the success of this reaction, generating a catalytic species that is significantly more active than simple nonsupported variants.

Despite recent progress in the catalytic transformation of inert phenol derivatives as alternatives to aryl halides and triflates, attempts at the cross-coupling of inert phenol derivatives with the C-H bonds of arenes have met with limited success. Herein, we report the rhodium-catalyzed cross-coupling of aryl carbamates with arenes bearing a convertible directing group. The key to success is the use of an in situ generated rhodium bis(N-heterocyclic carbene) species as the catalyst, which can promote activation of the inert C(sp )-O bond in aryl carbamates.

An ovel approach to the direct construction of tricyclic nitrogen heterocycles based on gold-catalyzed cascade cyclization of aminoallenynes is described. The expected biscyclization reaction of hydroxyisobutyryl-protected aminoallenynes was efficiently promoted by ac atalytic amount of BrettPhosAuNTf 2 in the presence of iPrOH to produce 1,2dihydrobenzo[cd]indole derivatives in good yields.W hen the reaction was combined with Friedel-Crafts acylation or palladium-catalyzed N-arylation, the resulting tricyclic products were efficiently converted into nitrogen-containing polycyclic aromatic compounds (N-PACs) with highly conjugated p-electron systems.Anewly obtained hexacyclic indolium salt showed characteristic concentration-dependent absorption and emission properties. Scheme 1. Gold(I)-catalyzed reactions of diynes and related compounds proceedingvia vinyl cation intermediates.

Concerted nucleophilic aromatic substitution (CSNAr) has emerged as a powerful mechanistic manifold, in which nucleophilic aromatic substitution can proceed in one step without the need to form a Meisenheimer intermediate. However, all of the CSNAr reactions reported thus far require a stoichiometric strong base or activating reagent, and no catalytic variants have yet been reported. Herein, we report an N‐heterocyclic carbene (NHC)‐catalyzed intramolecular cyclization of acrylamides that contain a 2‐fluorophenyl group on the nitrogen through a CSNAr reaction. By using this catalytic method, it is possible to synthesize an array of quinolin‐2‐one derivatives, which are common structural motifs in pharmaceuticals and organic materials. DFT calculations unambiguously revealed that this reaction proceeds through the concerted nucleophilic aromatic substitution of aryl fluorides, in which a stereoelectronic σ (Cipso‐Cβ)→ σ*(Cipso‐F) interaction critically contributes to the stabilization of the transition state for the cyclization.