Selective monohydrolysis of symmetric diesters and total synthesis of a series of pyrenyl maleimide fluorescent chemosensors

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2011-08

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Abstract

As an important desymmetriztion reaction, monohydrolysis facilitates modern synthetic organic chemistry by significantly shortening synthetic routes. Half esters produced by monohydrolysis play an important role in organic synthesis. In chapter 2, we studied the monohydrolysis of symmetric dialkyl benzendicarboxylates, including ortho-phthalate, meta-phthalate, para-phthalate. In addition to the stereochemical effect, the solubility was found to be a possible factor that would affect the selectivity of monohydrolysis. The ultrasound-assisted monohydrolysis of bulky symmetric diesters was also discussed in this chapter. Several bulky diesters were monohydrolyzed with ultrasound. We found out that it was possible to increase the reaction rate by ultrasound without decreasing selectivity. In chapter 3, a mechanism of monohydrolysis was proposed, and the possibility to prove the mechanism by measuring critical micelle concentrations of intermediates is discussed. In additional to the research on monohydrolysis, a synthetic study of a series of new and effective pyrenyl maleimide fluorescent probes for sampling of longer inter-thiol distances was also conducted. In chapter 4, the syntheses of pyrenylbutyl maleimide, pyrenyloctyl maleimide and pyrenyldecyl maleimide were discussed. Further spectroscopic characterization of pyrenylbutyl maleimide showed it was an excellent probe to assess proximities between cysteine in proteins or thiols in macromolecules, and to follow conformational changes.

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Keywords

Desymmetriztion, Monohydrolysis, Total synthesis, Pyrenyl maleimide

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