Preparation and Utilization of Chiral Synthons of Cyclopentadienone and Cyclohexadienone

环戊二烯酮和环己二烯酮手性合成物的制备及应用

• 批准号: 06672083
• 负责人: OGASAWARA Kunio
• 金额: $ 1.22万
• 依托单位: TOHOKU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06672083/
• 关键词: chiral building block; chiral cyclopentadienone synthon; chiral cyclohexadienone synthon; enantiocontrolled synthesis; enzymatic reaction; chiral ligand-metal complex catalyst; lipase-mediated reaction; meso-asymmetrization; キラルシクロペンタジエノンシントン; キラ

Chiral equivalents of cyclopentadienone and cyclohexadienone have been prepared by employing lipase-mediated asymmetric transesterification and hydrolysis and by employing chiral ligand-metal complex catalyst.Basis of the present investigation is the convex-face selective reaction on the enone system of tricyclic synthons having bicyclo [2.2.1] heptane framework and their cleavage by retro Diels-Alder reaction to regenerate the double bond originated from cyclopentadienone and cyclohexadienone precursors.The high functionality and versatile utilities of the chiral synthons of cyclopentadienone and cyclohexadienone prepared have been demonstrated by the syntheses of a wide variety of biologically active natural products such as alpha-aminoacids, terpenes, steroids, alkaloids, and polyketides.

利用脂肪酶介导的不对称酯交换反应和水解反应，以及手性配体-金属络合物催化剂，合成了环己二烯酮和环己二烯酮的手性等价物.本研究的基础是具有双环[2.2.1]庚烷骨架的三环二烯酮的烯酮体系的凸面选择性反应及其逆Diels-通过桤木反应使环己二烯酮和环己二烯酮前体的双键再生，所制备的环己二烯酮和环己二烯酮手性配体具有高功能性和多用途，已被广泛的生物活性天然产物的合成所证实例如α-氨基酸、萜烯、类固醇、生物碱和聚酮化合物。

项目成果

K.Ogasawara: "Enantiocontrolled Route to Natural Products Using Chiral Equivalents of Cyclopentenone and Cyclohexenone" Pure&Appl.Chem.66. 2119-2122 (1994)

K.Ogasawara：“使用环戊烯酮和环己烯酮的手性等价物获得天然产物的对映控制路线”纯

Takashi Kamikubo: "Concise Enantiocontrolled Synthesis of the A-Ring Precursor of Calcitriol from the Chiral Cyclohexadienone Synthon" J.Chem. Soc., Chem, Commun. 1951-1952 (1995)

Takashi Kamikubo：“从手性环己二烯酮合成物中简明对映控制合成骨化三醇的 A 环前体”J.Chem。

Tsutomu Sugahara: "Contra-Steric Diels-Alder Route to 3-Oxodicyclopentadiene and Meso 3,5-endo-Dihydroxy-4,5-dihydrodicyclopentadiene" Tetrahedron Lett. 37. 205-208 (1996)

Tsutomu Sugahara：“3-氧二环戊二烯和内消旋 3,5-内-二羟基-4,5-二氢二环戊二烯的反立体狄尔斯-桤木路线”四面体快报。

Y.Sugihara: "Palladium-mediated Homologation of Optically Active(E)-2-Chlorovinylcarbinols" Synlett. 665-666 (1994)

Y.Sugihara：“钯介导的光学活性 (E)-2-氯乙烯基甲醇的同系化”Synlett。

Takashi Kamikubo: "Concise Enantiocontrolled Synthesis of the A-Ring Precursor of Calcitriol from the Chiral Cyclohexadienone Synthon" J. Chem. Soc. Chem. Commun.1951-1952 (1995)

Takashi Kamikubo：“从手性环己二烯酮合成物中骨化三醇 A 环前体的简明对映控制合成”J. Chem。