| Herein,we present the compounds containing spiro skeleton used for asymmetric catalysis, and two parts of work were included .In the first section of this part, we introduced spiro skeleton compound: (S)- 1, 1′- spirodiindane- 7, 7′- diamine into L - proline to get two derivatives: (S, S, S)- 1, 1′- spirodiindane- 7- amine- 7′(pyrrolidine- 2- carboxylic )amide(4) and (S, S)- 1, 1′- spirodiindane- 7, 7′- bis(pyrrolidine- 2- carboxylic acid amide) (5). The two new organocatalysts were used for catalyzing asymmetric aldol reaction. We take the reaction of P-nitro benzaldehyde and acetone as model reaction to inspect the influence of reaction conditions, such as: solvent, temperature, amount of catalyst loading on the catalytic activity and optically selectivity of the two catalysts. It proved that solvents were not good for catalytic activity and optical selectivity especially for the latter. In fact, 33%ee was obtained without solvent, while only 7- 14%ee were found with either polar or apolor solvent. As to the effect of reaction temperature, a lower temperature seemed to benefit the results in a certain extent, for example, enatioselectivities increased from 33%, 38%, 45% to 52% when the reaction temperature decreased from 25, 0, -15 to -25℃, respectively. While, under the same reaction temperature, similar results were found when the catalyst loadings were decreased from 20%, 10%, 5%, 2% to 1%. It indicated the high catalytic activity of these two new catalysts. Asymmetric aldol reactions with other aldehydes were carried out under the optimized reaction conditions: -25℃, 1%catalyst loading in moderate enatioselectivity(76%ee) and high yield(92%). In conclusion, rigid spirobackbone was introduced to L- proline to obtain two orgnocatalysts and high catalytic activity while moderate enatioselectivity were obtained in the catalytic asymmetric aldol reaction. It is an interesting exploration in designing new structure of organocatalysts.In the second section, we focused on design and synthesis of chiral spiro[4, 4] nonane backbone ligands containing nitrogen for asymmetric catalysis. Firstly, spiro[4, 4]nonane- 1,6- dione, one chiral center included compound was synthesized as the mother ligand. In the first step, spiro skeleton inchiral ligand containing nitrogen was synthesized: through the reaction of spiro[4, 4]nonane- 1, 6- dione with hydroxylamine hydrochloride, spiro[4, 4]nonane- 1, 6- dioxime was obtained, followed up with hydrogenation catalyzed by Raney-Ni, spiro[4, 4]nonane- 1, 6- diamine was obtained. Salen ligand was prepared by reaction of the spirodiamine with 3, 5- dichlorosalicylalhedyde and single crystsl of the ligand was obtained. Then, we continued to focus on chiral spiro[4, 4]nonane skeleton ligands containing nitrogen: refering to the literatures, 5-(α-benzylethyl)aminoxalylhydrazine was used as resolution reagent and chiral spiro[4, 4]nonane-1, 6- dione was obtained as optically purity. Taken the chiral dione as the strating material, optically pure spiro[4, 4]nonane-1, 6- dioxime was prepared as chiral imine ligand. Then, we found that in the presence of the catalytic amount of iodine, aromatic amine and the spirodione can dehydrate to give ketimine product when refluxing in methylene dichloride, and aliphatic ketimine can be obtained by the reaction of the spirodione and aliphatic amine in the mixture solvent of ether and hexane in the presence of catalytic TiCl4. In totally, eight ketimine were synthesized, and three of them were selected to use as chiral ligands to catalyze asymmetric cyclopropanation of alkene with CuCl insitu. A series of new kind of IGRs (Insect Growth Regulations) containing carbamic acid ester and biphenyl ether unit are synthesized. Their structures have been identified by MS, 1HNMR, IR, This is expected to be useful and interesting exploration of new kind of insecticide of juvenile hormone analogs for agriculture.
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