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是对对映体选择串联羰基的异常有效的催化剂，与芳基乙烯烯，烷氧基乙烯，苯乙烯和二级二级联元素的2-二唑-3,6-二甲基植物的形成 - 载量反应，均具有芳基乙烯二烯烃，供应量的高高。 （2）通过与dirhodhodium（ii）复杂的复合物与Styrene和灵活的交叉链接的复合物相共聚合，可以实现高达99％EE的对映射性以及具有完美的Exo钻石选择性。固定的催化剂以-78℃的促催化剂促进了分子内C-H插入反应，具有高的对映选择性，可用于多达100个顺序应用，步行水平低（0.28 ppm）。（3）在Rawal的二烯和Aldemy and Aldely and and and the-bpt and the and rhpie and rhppi and the and rhpie and rhppi and rhppi and the and rhppi and s of 1摩尔的影响下（3）在用乙酰氯化物治疗后，给出了相应的二氢吡喃酮，最高为99％。

项目成果

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

Asymmetric Intermolecular N-H Insertion Reaction of Phenyldiazoacetates with Anilines Catalyzed by Achiral Dirhodium (II) Carboxylates and Cinchona Alkaloids

非手性二铑(II)羧酸盐和金鸡纳生物碱催化重氮乙酸苯基酯与苯胺的不对称分子间N-H插入反应

• 发表时间: 2010
• 期刊: Heterocycles
• 影响因子: 0.6
• 作者: H.Saito;et al
• 通讯作者: et al