| Our group is developing a general approach to photolabile molecular systems based on addition of 1,3-dithianes and related 1,3-dithioheterocycles to ketones and aldehydes. The goal of this thesis was to develop a method for the quantitative evaluation of the efficiency of the photofragmentation, synthesize a variety of the photolabile latches and estimate their potential for new designs of the photolabile systems.;Absolute quantum yields measurements employing benzophenone-benzhydrol actinometrical system were carried out to evaluate the efficiency of the photofragmentation.;It was shown, that replacement of the hydroxyl group with an amino-moiety either in the form of amines, ureas, or amides does not affect the photochemical reaction efficiency. In sterically-congested environments, 1,3,5-trithiane adducts are more efficient than 1,3-dithiane adducts.;Convenient and economical way of converting 1,n-diiodides and dibromides into 1,3-dithioheterocycles with borohydride/CS2 reagent was developed. A number of the 5-substituted 1,3-dithianes with carboxy and hydroxy functionalities, allowing for easy further modification were synthesized.;A novel family of amino acid-based 1,3,5-dithiazines was synthesized, and their compatibility with Corey-Seebach chemistry was tested. Efficiency of the photochemical fragmentation of the benzaldehyde adduct was determined.;Formation of the previously unknown 3,5-dithia-1-azabicyclo[2.2.1]heptanes was discovered. Desulfurization of adducts of the 3,5-dithia-1-azabicyclo[2.2.1]heptanes to carbonyl compounds provides a synthetic route to the diastereomerically pure 1,3-aminoalcohols.;The generality of the modular approach was demonstrated by design and synthesis of a variety of the crown-ethers based objects for molecular recognition utilizing a number of the dithiane and trithiane based building "blocks". A stepwise modular assembly of the blocks offers a straightforward approach to elaborate hybrid structures.;Photolabile latches bearing amino-functionality were designed and developed based on the amino-counterparts of Corey-Seebach adducts. The range of possible applications, thus, was greatly expanded because presence of the amino functionality allowed for creation of the photolabile molecular systems via peptide chemistry. |
