Development of versatile synthetic route for 1,2-diamines as excellent chiral auxiliary.

1.从2-咪唑酮合成1,2-二胺的通用路线。2-咪唑酮被证明是合成1,2-二胺的一个很好的组成部分。通过Br_2与2-咪唑酮的烯烃部分加成反应和随后的取代反应，可以合成多种反式4,5-二取代2-咪唑烷酮。水解转化为1,2-二胺也成功了。构象固定的2-咪唑烷酮手性助剂。本文采用环二烯与2-咪唑酮[4+2]环加成的方法，合成了两种立体拥挤的2-咪唑烷酮对映体，作为有效的手性助剂。揭示了这些助剂在烷基化反应、Diels-Alder反应和醛醇反应等不对称合成反应中的应用。1,2-二胺转化为2-咪唑啉。以氯氧磷为原料，通过脱水反应合成了2-咪唑类化合物。作为手性配体的进一步应用正在进行中。

1.Versatile Syunthetic Route for 1,2-Diamines from 2-Imidazolone.2-Imidazolone was proved to be a excellent building block for the synthesis of 1,2-diamines. Wide variety of trans-4,5-disubstituted 2-imidazolidinones could by synthesized by an addition reaction of Br_2 to the olefinic moiety of the 2-imidazolone and subsequent substitution reactions. Hydorlytic conversion to 1,2-diamines also succeeded.2.Conformationally Fixed 2-Imidazolidinones as Chiral Auxiliaries.Both enantiomers of sterically congested 2-imidazolidinones, which served as efficient chiral auxiliaries, were synthesized by [4+2] cycloaddition of cyclic dienes with 2-imidazolone. The utilities of these auxiliaries in asymmetric synthetic reactions such as alkylations, the Diels-Alder reactions and aldol ractions were revealed.3.Conversion of 1,2-Diamines to 2-Imidazolines.2-Imidazolines were synthesized by dehydration reactions of the amide derivatives of the 1,2-diamines by phosphorus oxychloride. Further applications as chiral ligands are now in progress.