Cavity Click Chemistry: Cavity-Catalyzed Azide–Alkyne Cycloaddition

Click chemistry, which refers to chemical reactions that are fast and selective with high product yields, has become a powerful approach in organic synthesis and chemical biology. Due to the cytotoxicity of the transition metals employed in click chemistry reactions, a search for novel metal-free alternatives continues. Herein, we demonstrate that an optical cavity can be utilized as a metal-free alternative in the click chemistry cycloaddition reaction between cyanoacetylene and formylazide using the quantum electrodynamics coupled cluster method. We show that by changing the molecular orientation with respect to the polarization of the cavity mode(s), the reaction can be selectively catalyzed to form a major 1,4-disubstituted or 1,5-disubstituted product. This work highlights that a cavity has the same effect on the investigated cycloaddition as the transition metal catalysts traditionally employed in click chemistry reactions. We expect our findings to further stimulate research on cavity-assisted click chemistry reactions

Synthesis and Use of 5-Vinyl-1,2,4-oxadiazoles as Michael Acceptors. A Rapid Synthesis of the Potent Muscarinic Agonist L-670,548

Synthesis and Use of 5-Vinyl-1,2,4-oxadiazoles as Michael Acceptors. A Rapid Synthesis of the Potent Muscarinic Agonist L-670,54

Dynamics of aggregation formation.

Timing of aggregation growth of Brachinus elongatulus during two experiments. In both experiments the daylight-simulating bulb came on at 4:15 AM. Experiment 1: beetles with one shelter to aggregate under (grey dotted line). Experiment 2: beetles with a choice of a shelter with five tethered conspecifics (blue line); a shelter with five tethered B. mexicanus (green line); and an empty shelter (red line).</p

Collecting locations.

Map of seven sites across central and southeast Arizona where whole aggregations of Brachinus were collected. For more details on each site see Table 1.</p

Maximum likelihood tree of concatenated matrix.

Outgroups not shown. Branches with bootstrap values >90 are thickened. The eight species found in multispecies aggregations in Arizona are highlighted in color. Asterisks denote specimens collected from multispecies aggregations. Grey triangles point to five species found in a single aggregation at Site 3.</p

Aggregation size distribution.

Size distribution of all 59 aggregations collected ordered from smallest to largest; average 19.2; median 10. Numbers above bars represent the collecting site (1-7) of each aggregation as shown in Table 1.</p

Aggregation type by site.

Number of single and multispecies aggregations found at each collecting site.</p

Species content by site.

Species content at each collecting site. The percent of aggregations that contained multiple species is indicated to the right of each bar. Percentages of individuals of each species found in multispecies aggregations are next to the species names in the legend. We collected 484 individuals at Site 7, the bar was truncated in this figure to aid visual comparison among sites.</p

Plaster shelters and arenas for aggregation experiments.

(a) Bottom of shelter showing amphitheater and entrance. (b) Front view of shelter showing entrance. (c) Arena with moistened sand substrate. Shelters positioned on the south side of the arena with their entrances facing north. (d) Three arenas set up with separators and daylight simulating bulbs hanging to the north. (e) Opaque curtain covering the south side of arenas.</p

Details of four choice experiments.

Details of four choice experiments.</p