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. 2012 Oct 21;10(39):7980-5.
doi: 10.1039/c2ob26571k.

Versatile approach to α-alkoxy carbamate synthesis and stimulus-responsive alcohol release

R Adam Mosey  1 , Paul E Floreancig
Affiliations

Versatile approach to α-alkoxy carbamate synthesis and stimulus-responsive alcohol release

R Adam Mosey et al. Org Biomol Chem. .

Abstract

A series of α-alkoxy carbamates that cleave under mild conditions to release alcohols has been synthesized through a multicomponent process. The relationship between structural features in these compounds and the rate of alcohol release in the presence of basic hydrogen peroxide has been studied. The preparation of carbamates that cleave under other conditions has been demonstrated.

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Figures

Fig. 1
Fig. 1
Schematic of a cargo-releasing composite structure that contains localization and triggering groups.
Fig. 2
Fig. 2
Time dependent release of neopentyl alcohol from 5. The AB pattern arises from 5 and the growing singlet arises from neopentyl alcohol. See Scheme 3 for experimental conditions.
Fig. 3
Fig. 3
Structurally-varied carbamates.
Fig. 4
Fig. 4
Comparison of the rates of alcohol release from structurally-varied nitrile precursors. See Scheme 3 for experimental conditions. Experiments were run in triplicate.
Fig. 5
Fig. 5
Impact of carbamate variation on alcohol release. See Scheme 3 for experimental conditions. Experiments were run in triplicate.
Fig. 6
Fig. 6
Release as a function of alcohol structure. See Scheme 3 for experimental conditions. Experiments were run in triplicate.
Fig. 7
Fig. 7
Release from the allylic carbamate. See Scheme 3 for experimental conditions. Experiments were run in triplicate.
Fig. 8
Fig. 8
PMC release from 28 in response to variations in pH and H2O2 concentration. Reactions were performed using 40 µM of 28 or 29 in 95% aqueous phosphate buffer/5% EtOH at 37 °C. Experiments were run in triplicate.
Scheme 1
Scheme 1
Stimulus-promoted cleavage of α-alkoxy carbamates.
Scheme 2
Scheme 2
Multicomponent approach to α-alkoxy carbamate synthesis.
Scheme 3
Scheme 3
Peroxide-mediated alcohol release. [5]0 = 6 mM, [H2O2]0 = 90 mM, T = 300 K.
Scheme 4
Scheme 4
Determination of an isolated yield.
Scheme 5
Scheme 5
Application to the synthesis of a potential mitigator of radiation damage.
See this image and copyright information in PMC

References

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