Highly Effective Chirality Controlling Systems.

高效的手性控制系统。

• 批准号: 07457614
• 负责人: KUNIEDA Takehisa
• 金额: $ 1.41万
• 依托单位: Kumamoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07457614/
• 关键词: 2-Amino alcohol; 2-Oxazolone; 2-Oxazolidinone; Asymmetric synthesis; Chiral auxiliary; 2-Imidazolone; 2-Imidazolidinone; Chiral synthesis

1.Chiral 2-Oxazolidinones and 2-Imidazolidinones Auxiliaries.Both enantiomers of sterically congested 2-oxazolidinones and 2-imidazolidinones, which served as efficient chiral auxiliaries, were synthesized by [4+2] cycloaddition of cyclic dienes with 2-oxazolone and 2-imidazolone. The utilities of these auxiliaries in asymmetric synthetic reactions such as alkylations, the Diels-Alder reactions, michael reactions and aldol reactions were revealed.2.Conformationally Fixed 2-Amino Alcohols.The 2-oxazolidinones, mentioned above, were hydrolyzed to conformationally fixed 2-amino alcohols of synthetic significance.(1) N,N-Dialkylamino alcohols and N-sulfonylamino alcohols served as equally effective catalysts in ethylation of aldehydes with ZnEt_2, but showed completely reversed enantioselectivity.(2) Lithium salts of N-sulfonylamino alcohols cleaved meso-dicarboxylic anhydrides to the half esters with almost perfect diastereoselectivity. In contrast, zinc salts reacted with the anhydrides with opposite selectivity.

1.手性2-恶唑烷酮和2-咪唑烷酮助剂。空间拥挤的2-恶唑烷酮和2-咪唑烷酮的两种对映体都是有效的手性助剂，通过环状二烯与2-恶唑酮和2的[4+2]环加成合成。 -咪唑酮。揭示了这些助剂在烷基化、狄尔斯-阿尔德反应、迈克尔反应和羟醛反应等不对称合成反应中的用途。2.构象固定的2-氨基醇。上述2-恶唑烷酮被水解为构象固定的2 -具有合成意义的氨基醇。(1) N,N-二烷基氨基醇和N-磺酰氨基醇在乙基化中作为同样有效的催化剂(2)N-磺酰氨基醇的锂盐以几乎完美的非对映选择性将内消旋二酸酐裂解为半酯。相反，锌盐与酸酐的反应具有相反的选择性。

项目成果

Tadao Ishizuka: "2-Oxazolone asBuilding Block for Chiral Auxiliaries -- Extremely Powerful Chiral 2-Oxazolidinone and 2-Aminoalcohol Auxiliaries --" Advances in Pharmaceutical Sciences. 12. 23 (1996)

Tadao Ishizuka：“2-恶唑酮作为手性助剂的构建模块——极其强大的手性 2-恶唑烷酮和 2-氨基醇助剂——”制药科学进展。

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。

T.Ishizuka: "Synthetic Application of Chiral 4-Methoxy-2-oxazolidinone Synthons to 2-Amino Alcohols of Biological Interest." Heterocycles. 42. 837-848 (1996)

T.Ishizuka：“手性 4-甲氧基-2-恶唑烷酮合成子在具有生物价值的 2-氨基醇中的合成应用”。

Tadao Ishizuka: "Synthetic Application of Chiral 4-Methoxy-2-oxazolidinone Synthons to 2-Amino Alcohols of Biological Interest." Heterocycles. 42. 837-848 (1996)

Tadao Ishizuka：“手性 4-甲氧基-2-恶唑烷酮合成子在具有生物价值的 2-氨基醇中的合成应用”。

Taiju Nakamura: "Stercially 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。