Alkynyl N-BODIPYs as Reactive Intermediates for the Development of Dyes for Biophotonics

Abstract

A new approach for the rapid multi-functionalization of BODIPY dyes towards biophotonics is reported. It is based on novel N-BODIPYs, through reactive intermediates with alkynyl groups to be further derivatized by click chemistry. This approach has been exemplified by the development of new dyes for cell bio-imaging, which have proven to successfully internalize into pancreatic cancer cells and accumulate in the mitochondria. The in vitro suitability for photodynamic therapy (PDT) was also analyzed and confirmed our compounds to be promising PDT candidates for the treatment of pancreatic cancer.

Dissimilar-at-boron N-BODIPYs: from light-harvesting multichromophoric arrays to CPL-bright chiral-at-boron BODIPYs

“…All these synthetic results, including our preliminary ones, 20 demonstrate the ease and versatility of constructing dissimilar-at-boron N -BODIPYs, as well as the utility of NBDP-8 (and related compounds) as a readily-accessible precursor of functionalized BODIPY dyes through workable click chemistry.…”

“…a FBDP-1 : 2,6-diethyl-1,3,5,7,8-pentamethyl- F -BODIPY; FBDP-2 : 2-ethyl-1,3,8-trimethyl- F -BODIPY.ba: Tosyl; b: butane-1-sulfonyl; c: anthracene-2-sulfonyl; d: (1 S )-camphor-10-sulfonyl; e: {4-[(propargyloxy)carbonyl]phenyl}sulfonyl.cChemical yield in the preparation of I from ethane-1,2-diamine.dChemical yield in the preparation of the N -BODIPY ( NBDP ) from the corresponding F -BODIPY ( FBDP ) and bis(sulfonamide) I .eRef. 20.…”

“…Finally, dissimilar-at-boron N -BODIPY NBDP-4 was obtained following the same procedure used preliminarily by us for the preparation of NBDP-2 and NBDP-3 . 20 This procedure involves first preparing the clickable ethynyl-based dissimilar-at-boron NBDP-8 20 from FBDP-1 and bis(sulfonamide) I-3 (see Table 1) to subsequently conduct a standard click reaction (CuSO 4 /sodium ascorbate) with the corresponding functionalized azide carrying the morpholino moiety (see Fig. 2).…”

“…1), as potential photodynamic therapy (PDT) agents based on specific organelle accumulation, where one of the sulfonylamino moieties dangling from boron was rationally selected to gain the desired biospecificity, and the other one to address solubility issues. 20 These preliminary results on the construction of dissimilarat-boron N-BODIPYs as a versatile BODIPY post-multifunctionalization approach prompted us to investigate its scope by the rationally-guided design and efficient (convergent) synthesis of a selected set of dissimilar-at-boron N-BODIPYs (see Fig. 1).…”

“…1), as potential photodynamic therapy (PDT) agents based on specific organelle accumulation, where one of the sulfonylamino moieties dangling from boron was rationally selected to gain the desired biospecificity, and the other one to address solubility issues. 20…”