Boron–Nitrogen Bond

António, João P. M.; Farias, Gonçalo D. V.; Santos, Fábio M. F.; Oliveira, Rudi; Cal, Pedro M. S. D.; Góis, Pedro M. P.

doi:10.1002/9781119113874.ch2

Cited by 2 publications

(1 citation statement)

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“…The formation of tetracyclic polycondensation adduct 4 , an isomer of 3 , is not merely a solid-state phenomenon; adduct 4 was analyzed by 11 B NMR spectroscopy in methanol (CD 3 OD), which revealed a sharp singlet with a chemical shift of 13.8 ppm (Figure S1) consistent with a neutral tetrahedral boronate adduct. This new structural information, which concurs with the current understanding of BN interactions, , further explains the lack of reversibility observed in our initial studies . Although future efforts will be necessary to assess product stability in physiological environments such as in serum and tissues, we believe that the formation of a tetracyclic adduct with an internal tetrahedral BN complex results in a boronate that is protected against hydrolysis, making this click chemistry practically irreversible.…”

Section: Resultssupporting

confidence: 80%

In Vivo Targeting Using Arylboronate/Nopoldiol Click Conjugation

et al. 2020

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Bioorthogonal click reactions yielding stable and irreversible adducts are in high demand for in vivo applications, including in biomolecular labeling, diagnostic imaging, and drug delivery. Previously, we reported a novel bioorthogonal “click” reaction based on the coupling of ortho-acetyl arylboronates and thiosemicarbazide-functionalized nopoldiol. We now report that a detailed structural analysis of the arylboronate/nopoldiol adduct by X-ray crystallography and 11B NMR reveals that the bioorthogonal reactants form, unexpectedly, a tetracyclic adduct through the cyclization of the distal nitrogen into the semithiocarbazone leading to a strong B–N dative bond and two new 5-membered rings. The cyclization adduct, which protects the boronate unit against hydrolytic breakdown, sheds light on the irreversible nature of this polycondensation. The potential of this reaction to work in a live animal setting was studied through in vivo capture of fluorescently labeled molecules in vivo. Arylboronates were introduced into tissues through intradermal injection of their activated NHS esters, which react with amines in the extracellular matrix. Fluorescently labeled nopoldiol molecules were administered systemically and were efficiently captured by the arylboronic acids in a location-specific manner. Taken together, these in vivo proof-of-concept studies establish arylboronate/nopoldiol bioorthogonal chemistry as a candidate for wide array of applications in chemical biology and drug delivery.

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Section: Resultssupporting

confidence: 80%