Selective access to dihydrophenanthridines and phenanthridinones cyclisation of aryl amines onto -tethered arynes.

5,6-Dihydrophenanthridines are prepared from aryl amines intramolecular addition to -tethered arynes under mild conditions. A new -silylaryl triflate precursor was developed to increase reactivity and enable electron-rich and electron-poor aryl amines to undergo cyclisation. A complete switch in product selectivity occurs when the reaction is conducted in air, affording the corresponding phenanthridin-6(5)-one as the sole product under otherwise identical reaction conditions.

There is no market for new antibiotics: this allows an open approach to research and development.

There is an increasingly urgent need for new antibiotics, yet there is a significant and persistent economic problem when it comes to developing such medicines. The problem stems from the perceived need for a "market" to drive commercial antibiotic development. In this article, we explore abandoning the market as a prerequisite for successful antibiotic research and development.

Synthesis of Highly Enantioenriched Sulfonimidoyl Fluorides and Sulfonimidamides by Stereospecific Sulfur-Fluorine Exchange (SuFEx) Reaction.

Sulfonimidamides present exciting opportunities as chiral isosteres of sulfonamides, with potential for additional directional interactions. Here, we present the first modular enantioselective synthesis of sulfonimidamides, including the first stereoselective synthesis of enantioenriched sulfonimidoyl fluorides, and studies on their reactivity. A new route to sulfonimidoyl fluorides is presented from solid bench-stable, N-Boc-sulfinamide (Boc=tert-butyloxycarbonyl) salt building blocks.

Intramolecular hydride transfer onto arynes: redox-neutral and transition metal-free C(sp)-H functionalization of amines.

Transition metal-free intramolecular hydride transfer onto arynes is reported for the first time. This unique transformation is utilized in redox-neutral intermolecular α-functionalization reactions of different tertiary amines, generating C(sp)-C(sp/sp/sp) bonds in a single synthetic operation. Deuterium labeling studies support initial cleavage of the α-C-H bond intramolecular 1,5-hydride transfer onto the aryne, which leads to activation of a range of integrated pronucleophiles and ultimately affords a new approach to cross-dehydrogenative coupling reactions which utilize aryne intermediates.

Recent advances in fluoride-free aryne generation from arene precursors.

Aryne chemistry has experienced a remarkable renaissance in recent years, with a significant increase in the synthetic applications reported for these highly valuable reactive intermediates. This resurgence of interest is in part due to the introduction of ortho-silylaryl triflates as precursors which can be activated under mild conditions using fluoride. Alternative fluoride-free strategies have received interest in the last decade, with a number of precursors to arynes and their activators reported.