Recognition Of Amine Derivative With Porphyrins Via Circular Dichroism And The Study Of Asymmetric Catalysis With Long-Chain Alkyl Amino Acid

Chirality is the motif of nature produancts, pesticides, and drugs. The chirality research mainly focus on the recognition, synthesis, and asymmetric catalysis. This thesis focus on the recognition, synthesis, and asymmetric catalysis of animo small molecules..First part:The absolute configuration of chiral compounds is determined with ruthenium porphyrin via a circular dichroism method. With the strong binding of metallic porphyrin and amines, Nakanishi group designed a bridge chain bimetallic porphyrin structure to associate with diamine. For the different size of different groups on the chiral carbon atom, the space structure become distorted arrangement. This can translate into circular dichroism spectrum signal. Based on Nakanishi’s resrearch, This thesis use a non-bridge-chain bisporphyrin to determine the chirality of small organic molecules vis circular dichroism:1. Our works found that ruthenium porphyrin has more stronger binding capacity with amines, so we use the free two porphyrins to bond with diamine to form host-guest sandwich structure. With this we can ascretain the chirality of small organic molecules by circular dichroism;2. With the same method, the chirality of amino alcohols is also determined through deriving with N-(tert-Butoxycarbonyl)ethanolamine to form a diamine-like structure.Second part:The asymmetric catalysis with chiral amino small molecule was studied. Five chiral amino molecular catalysts were derivated from aliphatic and aromatic amino acids with long alky] chain. Catalytic activity and stereoselectivity were researched systematically:1. Alanine, valine, and leucine, three aliphatic amino acids and phenylglycine, phenylalanine two aromatic amino acid were selected to be derivated with18carbon amine as side chain. Aldol condensation reaction of acetone and benzaldehydes in solvent-free cinditions was conducted;2. With the same catalyst, we observed Michael condensation raction with acetone and β-nitrostyrene.