Triple aryne–tetrazine reaction enabling rapid access to a new class of polyaromatic heterocycles

Abstract

One of the most challenging goals of modern synthetic chemistry is to develop multi-step reactions for rapid and efficient access to complex molecules. We report a triple aryne-tetrazine reaction that enables rapid access to a new class of polyaromatic heterocycles. This new reaction, which couples diverse reactivity modes between simple aryne and tetrazine starting materials, proceeds in a single operation and takes less than 5 minutes in air with no metal catalyst.

New Red‐Emitting Tetrazine‐Phenoxazine Fluorogenic Labels for Live‐Cell Intracellular Bioorthogonal Labeling Schemes

“…Parallel to this, methyltetrazine boronic acid pinacol ester ( 7 ) was synthesized from 3‐(4‐bromophenyl)‐6‐methyl‐1,2,4,5‐tetrazine obtained by a modified procedure reported by Chenoweth et al . and bis(pinacolato)diboron in 40 % yield.…”

“…A mixture of 3‐(4‐bromophenyl)‐6‐methyl‐1,2,4,5‐tetrazine (105 mg, 0.414 mmol, 1.0 equiv), commercially available bis(pinacolato)diboron (117 mg, 0.456 mmol, 1.1 equiv), [PdCl 2 (dppf)] (15 mg, 0.021 mmol, 0.05 equiv), and KOAc (61 mg, 0.622 mmol, 1.5 equiv) were suspended in 1,4‐dioxane (5 mL), and the suspension was heated at reflux for 2 h. After 2 h, the solution was cooled to room temperature, filtered through a Celite pad, and concentrated in vacuo. The residue was dissolved in CH 2 Cl 2 (20 mL) and washed with water (3×50 mL).…”

Cyclic Alkyne Approach to Heteroatom‐Containing Polycyclic Aromatic Hydrocarbon Scaffolds

“…One exciting application of arynes and cyclic alkynes lies in materials chemistry. Arynes have been employed in the synthesis of polymers and polycyclic aromatic hydrocarbons (PAHs), with the latter having a remarkable impact on the materials science field . PAHs have been used in widely‐used devices, such as organic light‐emitting diodes (OLEDs), field effect transistors (OFETs), and photovoltaics (OPVs) .…”

Cyclic Alkyne Approach to Heteroatom-Containing Polycyclic Aromatic Hydrocarbon Scaffolds

“…[1][2][3][4] Additionally,such efforts have led to ag reater understanding of aryne and cyclic alkyne reactivity and regioselectivities, [5][6][7] and ah ost of synthetic applications impacting catalysis, [8] agrochemistry, [9] pharmaceuticals,a nd academia. [12][13][14][15][16][17][18][19] One exciting application of arynes and cyclic alkynes lies in materials chemistry.A rynes have been employed in the synthesis of polymers and polycyclic aromatic hydrocarbons (PAHs), [2,[20][21][22][23] with the latter having aremarkable impact on the materials science field. [12][13][14][15][16][17][18][19] One exciting application of arynes and cyclic alkynes lies in materials chemistry.A rynes have been employed in the synthesis of polymers and polycyclic aromatic hydrocarbons (PAHs), [2,[20][21][22][23] with the latter having aremarkable impact on the materials science field.…”