Organic azides are still in the center of click chemistry connecting two molecules. However, taming the conjugation selectivity of azides is difficult without the help of the bulky groups. We...

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Organic azides are still in the center of click chemistry connecting two molecules. However, taming the conjugation selectivity of azides is difficult without the help of the bulky groups. We report herein the unique reactivities of α-azido secondary acetamides (α-AzSAs) as minimal and unhindered azide structures. The NH-azide interaction in the α-AzSAs, supposed by DFT calculation, allowed selective conjugation in the presence of other azido moieties. With Staudinger-Bertozzi ligation, α-AzSAs proceeded the conjugation prior to the other primary alkyl azides. On the other hand, in propargyl cationmediated triazole synthesis, other alkyl azides, including tertiary alkyl azides, underwent the conjugation faster than α-AzSAs. We also demonstrated discriminative integration of the functional components onto the diazide modular hubs. Figure 1. Multi-click Modular Hub Strategy Toward Multifunctional Materials, and Issues of Multi-Azides as Modular Hubs.

We report herein the unique reactivities of α-azido secondary acetamides (α-AzSAs) as minimal and unhindered azide structures. The NH–azide interaction in the α-AzSAs, supposed by DFT calculation, allowed selective conjugation in the presence of other azido moieties. With Staudinger-Bertozzi ligation, α-AzSAs proceeded the conjugation prior to the other primary alkyl azides. On the other hand, in propargyl cation-mediated triazole synthesis, other alkyl azides, including tertiary alkyl azides, underwent the conjugation faster than α-AzSAs. We also demonstrated discriminative integration of the functional components onto the diazide modular hubs.