Photolysis of vinylene thioxocarbonates: a new source of ketocarbenes

Torres, M.E.; Clement, A.; Strausz, O. P.

doi:10.1021/jo01299a054

Cited by 21 publications

(6 citation statements)

References 2 publications

(2 reference statements)

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“…Other routes to oxo carbenes (or carbenoids) are the a-elimination of bromine from a,a-dibromo ketones,96 the elimination of hydrogen bromide from a-bromo ketones,97 and the elimination of C02 or COS from dioxolenones (vinylene carbonates) or their sulfur analogues. 98 The first two reactios have not been investigated with regard to oxirene involvement; the third is discussed in HIE. The formation of an oxo carbene from a chlorooxirane and a dichlorooxirane was mentioned in IIIB.…”

Section: Very Low Yieldmentioning

confidence: 99%

Oxirenes

Lewars¹

1983

Chem. Rev.

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Section: Very Low Yieldmentioning

confidence: 99%

Oxirenes

Lewars¹

1983

Chem. Rev.

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“…Compared to the possible disadvantage of metal carbonyls, , which often have a background CO release due to the ligand exchange, metal-free organic photoCORMs captured great attention for highly controlled CO release. To date, several UV − , and visible light-activated photoCORMs such as cyclic aromatic α-diketone, a fluorescein analog: 6-hydroxy-3-oxo-3 H -xanthene-9-carboxylic acid, flavonols, − and 3-hydroxybenzo[g]quinolone frameworks were developed (see Figure a–c). However, these photoCORMs limit their practical usage in biomedical applications because of the cytotoxicity and limited tissue penetration (typically not more than 1 mm) ability of UV light.…”

Section: Introductionmentioning

confidence: 99%

One- and Two-Photon Uncaging of Carbon Monoxide (CO) with Real-Time Monitoring: On-Demand Carbazole-Based Dual CO-Releasing Platform to Test over Single and Combinatorial Approaches for the Efficient Regression of Orthotopic Murine Melanoma In Vivo

et al. 2022

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Herein, we report three new metal-free, photochemically active single, dual, and combinatorial CORMs (photoCORMs) based on a carbazole-fused 1,3-dioxol-2-one moiety which released one equivalent of CO, two equivalent of CO, and a combination of one equivalent of each CO and anticancer drug upon one- and two-photon excitation, respectively. The photoCORMs exhibited good cellular uptake and real-time monitoring ability of CO uncaging by a color change approach in cancerous B16F10 cells. Interestingly, the cytotoxicity assay on B16F10 cells indicated that the dual photoCORM has increased anticancer activity over the single and combinatorial photoCORMs upon irradiation. Our results also showed that CO could accelerate the effectiveness of the well-known anticancer drug (chlorambucil). Finally, the in vivo evaluation of the dual photoCORM on an established murine melanoma tumor (C57BL/6J mouse model) manifested a significant regression of tumor volume and led to significant improvement (>50%) in the overall survivability.

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“…Vinylene thioxocarbonates have been proposed as sources for the synthesis of ketenes and for mechanistic study of the Wolff rearrangement (WR). , Photolysis of o -phenylene thioxocarbonate ( 2 ) in an argon matrix with 270 nm light was studied by Torres et al This group reported the formation of cyclopentadienylketene with strong absorptions at 2133 and 2130 cm –1 upon excitation of this precursor. WR was assumed to proceed from the ketocarbene, but this species was not observed in the argon matrix studies.…”

Section: Resultsmentioning

confidence: 99%

Mechanistic Aspects of Ketene Formation Deduced from Femtosecond Photolysis of Diazocyclohexadienone, o-Phenylene Thioxocarbonate, and 2-Chlorophenol

et al. 2012

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The photochemistry of diazocyclohexadienone (1), o-phenylene thioxocarbonate (2), and 2-chlorophenol (3) in solution was studied using time-resolved UV-vis and IR transient absorption spectroscopies. In these three cases, the same product cyclopentadienyl ketene (5) is formed, and two different mechanistic pathways leading to this product are discussed: (a) rearrangement in the excited state (RIES) and (b) a stepwise route involving the intermediacy of vibrationally excited or relaxed carbene. Femtosecond UV-vis detection allows observation of an absorption band assigned to singlet 2-oxocyclohexa-3,5-dienylidene (4), and this absorption feature decays with an ∼30 ps time constant in hexane and acetonitrile. The excess vibrational energy present in nascent carbenes results in the ultrafast Wolff rearrangement of the hot species. IR detection shows that photoexcited o-phenylene thioxocarbonate (2) and 2-chlorophenol (3) efficiently form the carbene species while diazocyclohexadienone (1) photochemistry proceeds mainly by a concerted process.

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Photolysis of vinylene thioxocarbonates: a new source of ketocarbenes

Cited by 21 publications

References 2 publications

Oxirenes

Oxirenes

One- and Two-Photon Uncaging of Carbon Monoxide (CO) with Real-Time Monitoring: On-Demand Carbazole-Based Dual CO-Releasing Platform to Test over Single and Combinatorial Approaches for the Efficient Regression of Orthotopic Murine Melanoma In Vivo

Mechanistic Aspects of Ketene Formation Deduced from Femtosecond Photolysis of Diazocyclohexadienone, o-Phenylene Thioxocarbonate, and 2-Chlorophenol

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