Synthesis Of α-Diazophosphonates Derived From Chiral Natural Amino Acid And The Reaction Of Hydrogenation

The selective functionalization of carbon-hydrogen(C-H) bond is always the research hot spot of chemists. These reactions provide efficient strategy for synthesis of pharmaceuticals, natural products and other bioactive molecules. Moreover, diazocompounds are the most commonly used carbene intermediates or metal catalysts. Then varieties of chemical transformations can be proceeded, such as X-H(X=C, N, O, S, Si etc) insertions,cyclopropanations, ylide formations and 1,2-hydrogen migration reactions. Varieties of chemical compounds could be synthesized through these methods. In contrast to the extensive and fruitful studies of ɑ-diazo carboxylates, the research of ɑ-diazo phosphonates remain scare. It is known that organic phosphorous chemistry occupies an important position in life scientific research. What is more, organic phosphorous compounds exhibit extensive bioactivity and pharmaceutic activity. Among varieties of organic phosphorous compounds,β-amino phosphorus acids as the analogous of β-amino acids play an important role in organic phosphorus chemistry. Because they exhibits antibiotics, antivirius, weeding control, plant growth regulators and enzyme inhibit activities properties, the synthesis of β-amino phosphoric acids has become the research hot spot of chemists.In order to develop new method for the synthesis of β-amino phosphoric acids and synthesis some β-amino phosphoric acids with novel structures, we synthesized a series of novel α-diazo phosphonates derivatived from natural amino acid and hoped to utilize the reactive properties of theses α-diazo phosphonates to realize the above purpose. The author’s subject mainly involves the following specific contents:1. We got 14 α-diazo phosphonates(2a-2n) derivatived from natural amino acid through five or six procedure reactions which started from natural amino acids and further got 14β-amino phosphonate(3a-3n) by hydrogenation under 5% Pd-C catalytic reduction reaction,all 28 compounds were characterized by 1H NMR, 13 C NMR, 31 P NMR, mass spectrometry and high-resolution mass spectrometry.2. By measuring the optical rotation to calculate value of the specific rotation of the compound 28, wherein, regardless of the chiral amino acid is L-or D-optically active, the resulting diazo compound α-phosphonates are L optically active and β-amino phosphonate optically active and starting materials chiral natural amino acids optically active consistent.3. Preferred synthesis conditions of β-amino phosphonates is isopropanol as a solvent, a catalyst 5% Pd-C in an amount of 20% mol, the additive amount of glacial acetic acid was added to 60% mol, the reaction under a hydrogen atmosphere at room temperature for 2h.4. In experiments to explore ee value of β-amino phosphonate compounds found the ee of L-alanine derivatived β-amino phosphonate is 94.5%.