295
Chapter 10
Quantum-Chemical Investigation of Epoxidic
Compounds Transformation. Application
for In Vitro and In Vivo Processes Modeling
Sergiy Okovytyy
© Springer Science+Business Media Dordrecht 2014
L. Gorb et al. (eds.), Application of Computational Techniques in Pharmacy and Medicine,
Challenges and Advances in Computational Chemistry and Physics 17,
DOI 10.1007/978-94-017-9257-8_10
S. Okovytyy ()
Department of Organic Chemistry, Oles Honchar Dnipropetrovsk National University,
Dnipropetrovsk 49010, Ukrain
e-mail: sokovyty@icnanotox.org
Abstract Transformation of epoxides is a key step for numerous processes important both for synthetic organic chemistry and biochemistry. Since experimental
methods are restricted by the fixation of source compounds, intermediates and products of reactions, quantum chemical calculations serve as the only direct approach
for prediction of the structure and energy of transition states thus clarifying detailed
mechanisms of chemical reactions. This chapter summarizes results of quantum
chemical investigation of epoxides transformation mechanisms in alkaline, neutral
and acidic environments. Special attention has been paid to stereo- and regiochemistry of the processes, influence of solvation effects and nature of catalytic action of
mono- and bidentate acids.
10.1 Introduction
Epoxides play important role in the synthesis of wide row of chemicals and pharmaceutical intermediates [1]. Owing to the presence of heteroatom and high strain
energy of three-membered ring (119 kJ/mol [2]) oxiranes possess much higher reactivity if compare to acyclic analogs which results in easy C–O bond rupture [3–6]
through where disadvantage of a highly basic leaving group is compensated by significant decreasing of oxirane ring strain during reaction [7]. In addition to nucleophilic opening reactions epoxides can undergo elimination resulted in formation of
allylic alcohols [8, 9]. In acidic medium or in the presence of Lewis acids ring opening reaction can be accompanied by rearrangement to carbonyl compounds [10].
Chapter 10
Quantum-Chemical Investigation of Epoxidic
Compounds Transformation. Application
for In Vitro and In Vivo Processes Modeling
Sergiy Okovytyy
© Springer Science+Business Media Dordrecht 2014
L. Gorb et al. (eds.), Application of Computational Techniques in Pharmacy and Medicine,
Challenges and Advances in Computational Chemistry and Physics 17,
DOI 10.1007/978-94-017-9257-8_10
S. Okovytyy ()
Department of Organic Chemistry, Oles Honchar Dnipropetrovsk National University,
Dnipropetrovsk 49010, Ukrain
e-mail: sokovyty@icnanotox.org
Abstract Transformation of epoxides is a key step for numerous processes important both for synthetic organic chemistry and biochemistry. Since experimental
methods are restricted by the fixation of source compounds, intermediates and products of reactions, quantum chemical calculations serve as the only direct approach
for prediction of the structure and energy of transition states thus clarifying detailed
mechanisms of chemical reactions. This chapter summarizes results of quantum
chemical investigation of epoxides transformation mechanisms in alkaline, neutral
and acidic environments. Special attention has been paid to stereo- and regiochemistry of the processes, influence of solvation effects and nature of catalytic action of
mono- and bidentate acids.
10.1 Introduction
Epoxides play important role in the synthesis of wide row of chemicals and pharmaceutical intermediates [1]. Owing to the presence of heteroatom and high strain
energy of three-membered ring (119 kJ/mol [2]) oxiranes possess much higher reactivity if compare to acyclic analogs which results in easy C–O bond rupture [3–6]
through where disadvantage of a highly basic leaving group is compensated by significant decreasing of oxirane ring strain during reaction [7]. In addition to nucleophilic opening reactions epoxides can undergo elimination resulted in formation of
allylic alcohols [8, 9]. In acidic medium or in the presence of Lewis acids ring opening reaction can be accompanied by rearrangement to carbonyl compounds [10].