Triazole-phosphine Pd(II)-Enabled Dehydrogenation of Alcohols or Amines: A Combination of Experimental and Theoretical Study

We describe a novel triazole-phosphine Pd(II) (TPP) complex-catalyzed dehydrogenation reaction of alcohols or amines by using iodobenzene as the oxidant, in which a unique butterfly TPP dimer is first prepared via a three-component reaction of 1,2,3-triazole, P(Cy)3, and PdCl2 and the competitive cross-coupling reaction of iodobenzene with alcohols or amines could be avoided under TPP catalysis. In particular, the primary alcohols and imines can be further oxidized into acids or nitriles in a tunable manner, respectively. Preliminary mechanistic results by density functional theory calculation suggest that this reaction follows the Pd(II)–Pd(IV) catalytic pathway and the process of TPP-catalyzed oxidation dehydrogenation of alcohol or amine to form unsaturated bonds and Pd(II)–H species generated before the oxidative addition of TPP with iodobenzene, thereby avoiding competitive cross-coupling

Triazole-phosphine Pd(II)-Enabled Dehydrogenation of Alcohols or Amines: A Combination of Experimental and Theoretical Study

We describe a novel triazole-phosphine Pd(II) (TPP) complex-catalyzed dehydrogenation reaction of alcohols or amines by using iodobenzene as the oxidant, in which a unique butterfly TPP dimer is first prepared via a three-component reaction of 1,2,3-triazole, P(Cy)3, and PdCl2 and the competitive cross-coupling reaction of iodobenzene with alcohols or amines could be avoided under TPP catalysis. In particular, the primary alcohols and imines can be further oxidized into acids or nitriles in a tunable manner, respectively. Preliminary mechanistic results by density functional theory calculation suggest that this reaction follows the Pd(II)–Pd(IV) catalytic pathway and the process of TPP-catalyzed oxidation dehydrogenation of alcohol or amine to form unsaturated bonds and Pd(II)–H species generated before the oxidative addition of TPP with iodobenzene, thereby avoiding competitive cross-coupling

Acid-Activatable Theranostic Unimolecular Micelles Composed of Amphiphilic Star-like Polymeric Prodrug with High Drug Loading for Enhanced Cancer Therapy

Stimuli-responsive nanomedicine with theranostic functionalities with reduced side-effects has attracted growing attention, although there are some major obstacles to overcome before clinical applications. Herein, we present an acid-activatable theranostic unimolecular micelles based on amphiphilic star-like polymeric prodrug to systematically address typical existing issues. This smart polymeric prodrug has a preferable size of about 35 nm and strong micellar stability in aqueous solution, which is beneficial to long-term blood circulation and efficient extravasation from tumoral vessels. Remarkably, the polymeric prodrug has a high drug loading rate up to 53.1 wt%, which induces considerably higher cytotoxicity against tumor cells (HeLa cells and MCF-7 cells) than normal cells (HUVEC cells) suggesting a spontaneous tumor-specific targeting capability. Moreover, the polymeric prodrug can serve as a fluorescent nanoprobe activated by the acidic microenvironment in tumor cells, which can be used as a promising platform for tumor diagnosis. The superior antitumor effect in this <i>in vitro</i> study demonstrates the potential of this prodrug as a promising platform for drug delivery and cancer therapy