Development and Utilization of Versatile Chirl Building Blocks

多功能Chirl积木的开发和利用

• 批准号: 10557205
• 负责人: OGASAWARA Kunio
• 金额: $ 8.19万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10557205/
• 关键词: chiral building block; substrate-controlled synthesis; diastereocontrolled synthesis; enantiocontrolled synthesis; natural product synthesis; asymmetric synthesis; enzymatic resolution; kinetic resolution; キラルシクロペンタジエノン; キラルシクロヘキサジエノン; 触媒的分割; 酵

During the present investigation, three versatole chiral building blocks exhibiting convex-face selectivity have been developed by employing either enzymatic or chemical kinetic resolution method. All building blocks possess an enone and a masked enone moieties which allowed diastereocontrolled modification owing to their inherent stereochemical nature. Versatility of these chiral molecules as chiral building blocks were demonstrated by enantio- and diastereocontrolled construction of a variety of physiologically active natural products synthesized in the present investigation are prostaglandins (key intermediate), (-)-morphine, (+)-tanikolide, (-)-malyngolide, (-)-kainic acid, (+)-febrifugine, (+)- and (-)-levoglucosenone, (-)-shikimic acid, (-)-semburine, (-)-antirhine, (-)-quinine (key intermediate), (+)-uleine, (-)-aristeromycin, (+)-arnicenone, (-)-physostigmine, (-)-physovenine, (-)-aphanorphine, (-)-iridolactone, (+)-pedicularis-lactone, simplactone A, (-)-tetrahydrolipstatin, eight aldohexoses, six conduritols, pseudomonic acids, ferruginol, (+)-20R-dihydrocleavamine, (-)-quebrachamine, (-)-menisdaurilide, (-)-mesembrine, and (+)-sceletinum A.

在本研究中，三个具有凸面选择性的versatole手性积木已开发采用酶或化学动力学拆分方法。所有结构单元都具有烯酮和掩蔽的烯酮部分，由于其固有的立体化学性质，这些部分允许非对映体控制的修饰。这些手性分子作为手性结构单元的多功能性通过本研究中合成的各种生理活性天然产物的对映体和非对映体控制的结构来证明，这些天然产物是野牡丹素（关键中间体），（-）-吗啡，（+）-taniklavine，（-）-malyngolide，（-）-红藻氨酸，（+）-febrifugine，（+）-和（-）-左旋葡萄糖酮，（-）-莽草酸，（-）-三尖杉碱，（-）-安替比林，（-）-奎宁（关键中间体），（+）-乌来因，（-）-阿替霉素，（+）-阿尼烯酮，（-）-毒扁豆碱，（-）-毒扁豆碱，（-）-aphanorphine，（-）-虹彩内酯，（+）-pediculanide-内酯，辛普拉酮A，（-）-四氢lipstatin，八种醛己糖，六种Conduritols，假单胞菌酸，ferruginol，（+）-20R-二氢裂解胺，（-）-白坚木胺、（-）-蝙蝠葛内酯、（-）-mesembrine和（+）-sceletinum A。

项目成果

Masatoshi Honzumi 他2名: "A New Convergent Route to Aldohexoses from a Common Chiral Building Block"Org. Lett.. 3・9. 1355-1358 (2001)

Masatoshi Honzumi 和其他 2 人：“从常见手性构建模块到己醛糖的新收敛路线”Org. 3・9。

Keigo Tanaka, Takahiko Taniguchi, Kunio Ogasawara: "7,7-Dimethyl-6,8-dioxabicyclo [3,3.0] oct-3-en-2-one as a synthetic equivalent ketodicyclojpentadiene: a new route to (-)-physostigmine, (-) -physovenine, and (-)-aphanorphine"Tetrahedron Lett.. 42. 1049

Keigo Tanaka、Takahiko Taniguchi、Kunio Ogasawara：“7,7-二甲基-6,8-二氧杂双环 [3,3.0] oct-3-en-2-one 作为酮二环戊二烯的合成等效物：(-)-毒扁豆碱的新途径

Hideyuki Tanaka他5名: "Enantio-and diastereocontrolled synthesis of(-)-iridolactone and (+)-pedicularis-lactone"Orb.Lett.. 3・5. 679-681 (2001)

Hideyuki Tanaka 等 5 人：“(-)-iridolactone 和 (+)-pedillaryis-lactone 的对映体和非对映体控制合成”Orb.Lett.. 679-681 (2001)。

Hiromi Nakashima 他3名: "A Stereocontrolled Route to (-)-Epibatidine Using a Chiral cis-Cyclohexadiene-1,4-diol Equivalent"Synlett. 1405-1406 (1999)

Hiromi Nakashima 和其他 3 人：“使用手性顺式环己二烯-1,4-二醇等效物实现 (-)-Epibatidine 的立体控制路线”Synlett 1405-1406 (1999)。

Yosuke Iura, Tsutomu Sugahara, Kunio Ogasawara: "Enantio- and Diastereocontrolled Synthesis of an Angular Triquinane Sesquiterpene (+) -Arnicenone"Org. Lett.. 3. 291-293 (2001)

Yosuke Iura、Tsutomu Sugahara、Kunio Ogasawara：“角三奎烷倍半萜 ( ) -Arnicenone 的对映体和非对映体控制合成”Org。