16717-64-9Relevant articles and documents
Efficient Far-Red/Near-IR Absorbing BODIPY Photocages by Blocking Unproductive Conical Intersections
Shrestha, Pradeep,Dissanayake, Komadhie C.,Gehrmann, Elizabeth J.,Wijesooriya, Chamari S.,Mukhopadhyay, Atreyee,Smith, Emily A.,Winter, Arthur H.
, p. 15505 - 15512 (2020)
Photocages are light-sensitive chemical protecting groups that give investigators control over activation of biomolecules using targeted light irradiation. A compelling application of far-red/near-IR absorbing photocages is their potential for deep tissue activation of biomolecules and phototherapeutics. Toward this goal, we recently reported BODIPY photocages that absorb near-IR light. However, these photocages have reduced photorelease efficiencies compared to shorter-wavelength absorbing photocages, which has hindered their application. Because photochemistry is a zero-sum competition of rates, improvement of the quantum yield of a photoreaction can be achieved either by making the desired photoreaction more efficient or by hobbling competitive decay channels. This latter strategy of inhibiting unproductive decay channels was pursued to improve the release efficiency of long-wavelength absorbing BODIPY photocages by synthesizing structures that block access to unproductive singlet internal conversion conical intersections, which have recently been located for simple BODIPY structures from excited state dynamic simulations. This strategy led to the synthesis of new conformationally restrained boron-methylated BODIPY photocages that absorb light strongly around 700 nm. In the best case, a photocage was identified with an extinction coefficient of 124000 M-1 cm-1, a quantum yield of photorelease of 3.8%, and an overall quantum efficiency of 4650 M-1 cm-1 at 680 nm. This derivative has a quantum efficiency that is 50-fold higher than the best known BODIPY photocages absorbing >600 nm, validating the effectiveness of a strategy for designing efficient photoreactions by thwarting competitive excited state decay channels. Furthermore, 1,7-diaryl substitutions were found to improve the quantum yields of photorelease by excited state participation and blocking ion pair recombination by internal nucleophilic trapping. No cellular toxicity (trypan blue exclusion) was observed at 20 μM, and photoactivation was demonstrated in HeLa cells using red light.
Linking of Alcohols with Vinyl Azides
Wang, Yi-Feng,Hu, Ming,Hayashi, Hirohito,Xing, Bengang,Chiba, Shunsuke
, p. 992 - 995 (2016)
A protocol to link alcohols with vinyl azides has been established through fluoro- or bromo-alkoxylation of vinyl azides to provide α-alkoxy-β-haloalkyl azides. A series of primary and secondary alcohols including natural products and their derivatives such as sugars and steroids were successfully anchored with vinyl azides. The as-prepared cyanine dye linked testosterones were capable of rapid cell membrane imaging in real time.
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Hortmann,A.G. et al.
, p. 322 - 324 (1972)
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An aryl thiol-vinyl azide coupling reaction and a thiol-vinyl azide coupling/cyclization cascade: efficient synthesis of β-ketosulfides and arene-fused 5-methylene-2-pyrrolidinone derivatives
Wang, Yong,Wang, Yu-Jiao,Liang, Xian-Chen,Shen, Mei-Hua,Xu, Hua-Dong,Xu, Defeng
supporting information, p. 5169 - 5176 (2021/06/21)
The addition reaction of thiol to vinyl azide has been extensively studied. Variously substituted aryl thiols are all viable for this coupling process. The scope of the other partner is successfully expanded from α-aryl vinyl azide to α-alkyl vinyl azide.
Electrochemical Oxidative Cross-Coupling between Vinyl Azides and Thiophenols: Synthesis ofgem-Bisarylthio Enamines
Li, Guodong,Yu, Ke,Yang, Jiajun,Xu, Bo,Chen, Qianjin
, p. 15946 - 15952 (2021/07/20)
An electrochemical radical strategy involving alkene substrates provides a powerful approach for alkene functionalization. Herein, we described the first electrochemical synthesis ofgem-bisarylthio enamines from vinyl azides and thiophenols through the C-
