Graduation Year
2012
Document Type
Dissertation
Degree
Ph.D.
Degree Granting Department
Chemistry
Major Professor
Jon Antilla
Keywords
amino phosphine oxides, desymmetrization, hydroxy sulfides, N,S-acetals, organocatalysis
Abstract
The research presented in this dissertation focuses on chiral BINOL metal phosphatephosphoric acid catalyzed enantioselective additions of phosphorus and sulfur nucleophiles to imines and epoxides. In chapter 2, we reported a new method to synthesize chiral amino phosphine oxides. The reaction combines N-substituted imines and diphenylphosphine oxide catalyzed by chiral magnesium 9-antryl phosphate. A wide variety of aliphatic and aromatic aldimines substituted by electron neutral benzhydryl or dibenzocycloheptene groups were excellent substrates for the addition reaction. The imines protected with dibenzocycloheptene protecting group provided better enantioselectivity than those protected with benzhydryl group, while both imines gave comparable yields. Also, the substituted diphenylphosphine oxides were excellent nucleophiles obtaining chiral α-amino phosphine oxides in good yields and enantioselectivities.
In chapter 3, we reported the first catalytic asymmetric method to prepare enantioenriched N,S-acetals catalyzed TRIP phosphoric acids. The reaction combined N-acyl imines with thiols to generate products in excellent yield and enantioselectivity. Electron-rich and electron-deficient aromatic N-acyl imines were excellent substrate for the addition reaction. A wide range of aliphatic and aromatic thiols obtained the N,S-acetals in excellent yields and enantioselectivities.
The TRIP phosphoric acid was found to be an extremely efficient catalyst for the transformation, resulting in asymmetric induction at extremely low catalyst loading.
In chapter 4, a highly enantioselective method for desymmetrization of meso-epoxides using thiols catalyzed by substituted BINOL lithium phosphate is reported. This is the first example of epoxide activation using metal phosphate is reported. Various five and six membered aliphatic cyclic meso-epoxides were excellent substrates for the desymmetrization reaction; aromatic acyclic epoxides also reacted with excellent yield and asymmetric induction. Similarly electron rich and electron deficient aromatic thiols obtained the β-hydroxyl sulfides in excellent yields and enantioselectivities.
Scholar Commons Citation
Ingle, Gajendrasingh, "Chiral BINOL Metal Phosphate/Phosphoric Acid Catalyzed Enantioselective Addition of Phosphorus and Sulfur Nucleophiles to Imines and Epoxides" (2012). USF Tampa Graduate Theses and Dissertations.
https://digitalcommons.usf.edu/etd/4339
