Highly Enantioselective Reactions and Asymmetric Synthesis of Biologically Active Compounds

生物活性化合物的高度对映选择性反应和不对称合成

• 批准号: 20390002
• 负责人: HASHIMOTO Shunichi
• 金额: $ 12.48万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2008
• 资助国家: 日本
• 起止时间: 2008 至 2010
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-20390002/
• 关键词: 合成化学; 不斉触媒反応; 固相遷移金属; ロジウム(II)錯体; ラジカル重合反応; 1,3-双極付加環化反応; ヘテロDiels-Alder反応; カルベン; カルボニルイリド; ナイトレン; ルイス酸触媒; 高分子担持型錯体; C-H挿入反応; Rawalジエン

(1) Rh_2(S-TCPTTL)_4 is an exceptionally effective catalyst for enantioselective tandem carbonyl ylide formation-cycloaddition reactions of 2-diazo-3,6-diketoesters with arylacetylene, alkoxyacetylene, and styrene dipolarophiles, providing cycloadducts in good to high yields and with enantioselectivities of up to 99% ee as well as with perfect exo diastereoselectivity for styrenes.(2) A highly effective immobilization of Rh_2(S-PTTL)_4 has been achieved by copolymerization of dirhodium(II) complex-containing monomer with styrene and a flexible cross-linker. The immobilized catalyst promoted the intramolecular C-H insertion reaction at -78℃ with high enantioselectivity, and could be used for up to 100 sequential applications with a low leaching level (0.28 ppm).(3) The hetero-Diels-Alder reaction between Rawal's diene and aldehydes under the influence of 1 mol % of Rh_2(S-BPTPI)_4 proceeded cleanly and gave, after treatment with acetyl chloride, the corresponding dihydropyranones in up to 99% ee.

(1) Rh_2(S-TCPTTL)_4是2-重氮-3,6-二酮酯与芳基乙炔、烷氧乙炔和苯乙烯双极性试剂的对映选择性串联羰基形成-环加成反应中非常有效的催化剂，可提供高收率的环加合物，对映选择性高达99% ee，对苯乙烯具有良好的外非对映选择性。(2)采用含dihodium （II）配合物单体与苯乙烯和柔性交联剂共聚的方法，实现了Rh_2(s- ptl)_4的高效固定化。该固定化催化剂在-78℃下促进了分子内C-H插入反应，具有较高的对映选择性，可在低浸出水平（0.28 ppm）下连续应用多达100次。(3)在1mol %的Rh_2(S-BPTPI)_4的影响下，Rawal的二烯与醛的杂diols - alder反应干净，经乙酰氯处理后，相应的二氢吡喃酮含量高达99%。

项目成果

Polymer-Supported Chiral Dirhodium(II) Complex: Highly Durable and Recyclable Catalyst for Asymmetric Intramolecular C-H Insertion Reactions

聚合物支持的手性二铑(II)络合物：用于不对称分子内C-H插入反应的高度耐用且可回收的催化剂

• DOI: 10.1002/anie.201003730
• 发表时间: 2010
• 期刊: Angew. Chem. Int. Ed.
• 作者: Takeda;K.; Oohara;T.; Anada;M.; Nambu;H.; Hashimoto;S.
• 通讯作者: S.

Asymmetric synthesis of neolignans (-)-epi-conocarpan and (+)-conocarpan via Rh(II)-catalyzed C-H insertion process and revision of the absolute configuration of (-)-epi-conocarpan.

• DOI: 10.1021/jo900502d
• 发表时间: 2009-06-05
• 期刊: The Journal of organic chemistry
• 作者: Natori Y;Tsutsui H;Sato N;Nakamura S;Nambu H;Shiro M;Hashimoto S
• 通讯作者: Hashimoto S

Catalytic Asymmetric Construction of the 7-exo-Aryl-6,8-dioxabicyclo[3.2.1]octane Framework of Psoracorylifols B and C Using a Carbonyl Ylide Cycloaddition Strategy

利用羰基叶立德环加成策略催化不对称构建补骨脂酚 B 和 C 的 7-外-芳基-6,8-二氧杂双环[3.2.1]辛烷骨架

• DOI: 10.5012/bkcs.2010.31.03.694
• 发表时间: 2010
• 期刊: Bull. Korean Chem. Soc.
• 作者: Kurosaki;Y.; Shimada;N.; Anada;M.; Nambu;H.; Hashimoto;S.
• 通讯作者: S.

二核ロジウム(II)錯体の創製を基盤とする触媒的不斉合成反応

基于双核铑(II)配合物的催化不对称合成反应

• 作者: 浅場明莉;菊水健史;橋本俊一
• 通讯作者: 橋本俊一

Catalytic Asymmetric Construction of the 7-exo-Ary1-6,8-dioxabicyclo[3.2.1]octane Framework of Psoracorylifols B and C Using a Carbonyl Ylide Cycloaddition Strategy

利用羰基叶立德环加成策略催化不对称构建补骨脂酚 B 和 C 的 7-exo-Ary1-6,8-二氧杂双环[3.2.1]辛烷骨架

• 发表时间: 2010
• 期刊: Bulletin of the Korean Chemical Society
• 影响因子: 1.7
• 作者: Y.Kurosaki;et al
• 通讯作者: et al