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

开发 1,2-二胺作为优异手性助剂的通用合成路线。

• 批准号: 08672431
• 负责人: ISHIZUKA Tadao
• 金额: $ 1.22万
• 依托单位: Kumamoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08672431/
• 关键词: 2-Imidazolone; 2-Imidazolidinone; 1,2-Diamine; Optical resolution; Chiral auxiliary; Chiral synthesis; 1,2-ジアミン

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.

1.由2-咪唑啉酮合成1，2-二胺的多功能合成路线。2-咪唑啉酮被证明是合成1，2-二胺的一种优良的结构单元。通过Br_2与2-咪唑啉酮的烯键加成反应和随后的取代反应，可以合成出多种反式-4，5-二取代2-咪唑啉酮。2.构象固定的2-咪唑烷酮手性助剂通过环二烯与2-咪唑酮的[4+2]环加成反应，合成了两种具有空间构象的手性助剂2-咪唑烷酮对映体。这些助剂在烷基化反应、Diels-Alder反应、羟醛缩合反应等不对称合成反应中具有重要的应用价值。3. 1，2-二胺转化为2-咪唑啉。作为手性配体的进一步应用正在进行中。

项目成果

Takehisa Kunieda: "Synthetic Veresatality of 2-Oxazolone Heterocycle for Stereo-contraolled Construction of 2-Amino Alcohols." J.Synth.Org.Chem.,Jpn. 55. 1018-1028 (1997)

Takehisa Kunieda：“用于 2-氨基醇立体控制构建的 2-恶唑酮杂环的合成 Veresatality”。

Tadao Ishizuka: "Highly Efficient Chiral Auxiliaries : Sterically Constrained 2-Oxazolidinones and Derived Amino Alcohols" Reviews on Heteroatom Chemistry. 15. 227-241 (1996)

Tadao Ishizuka：“高效手性助剂：空间约束的 2-恶唑烷酮和衍生氨基醇”杂原子化学评论。

Noriaki Hashimoto: "The Highly Enantioselective Borane Reduction of Ketones Catalyzed by Chiral Oxazaboloridine Derived from Sterically Constrained Amino Aocohols" Heterocycles. 46. 189-192 (1997)

Noriaki Hashimoto：“由空间约束氨基醇衍生的手性 Oxazaboloridine 催化酮的高度对映选择性硼烷还原”杂环。

Taiju Nakamura: "Sterically Constrained Tricyclic 2-Oxazolidinone as Excellent Chiral Auxiliary" Tetrahedron Lett.38. 559-562 (1997)

Taiju Nakamura：“空间约束的三环 2-恶唑烷酮作为优秀的手性辅助剂”四面体 Lett.38。

Takehisa Kunieda: "Synthetic Versatility of 2-Oxazolone Heterocycle for Stereo-Controlled Construction of 2-Amino Alcohols." J. Synth. Org. Chem., Jpn.55. 1018-1028 (1997)

Takehisa Kunieda：“2-恶唑酮杂环的合成多功能性用于立体控制 2-氨基醇的构建。”