Development of asymmetric reactions using multi-reagent complexes

使用多试剂复合物开发不对称反应

• 批准号: 15390005
• 负责人: TOMIOKA Kiyoshi
• 金额: $ 9.73万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15390005/
• 关键词: lithium enolate; chiral diether ligand; Taxol; asymmetric addition; aryllithium; tandem reactions; (-)-lycorine; chiral amidophosphine; 三成分複合反応剤; 閉環反応; キラルアミドモノホスフィン

1)A precursor of Taxol side chain was stereoselectively synthesized in high yield by the oxidation of the dianion resulting from the asymmetric addition of a chiral lithium enolate, derived from a chiral acetate, to N-PMP imine in the presence of a lithum amide.2)A formal total synthesis of (-)-1-deoxylycorine was achieved using tandem conjugate addition-cyclization reaction of aryllithium and alkenoate controled by a chiral ligand.3)5-Arylcyclohexenones and trans-3,6-disubstituted cyclohexanons were synthesized with high stereoselectivity in good yields using an amidophosphane-rhodium catalyzed asymmetric addition of arylborane reagents to substituted cyclohexenones.4)Chiral amino alcohol controlled asymmetric addition of alkynylzincs to nitroalkenes and aldehydes was developed.5)Chiral oxazoline ligand controlled catalytic asymmetric intramolecular hydroamination was developed.6)Chiral amidophosphane ligand controlled asymmetric addition of dialkylzincs to nitroalkene was developed.7)A formal synthesis of (+)-halichlorine was achieved using tandem Michael addition-alkylation protocol controlled by a chiral diether ligand.

1)在酰胺锂存在下，通过手性烯醇锂与N-PMP亚胺的不对称加成反应，氧化二价阴离子，以高产率立体选择性地合成了紫杉醇侧链的前体。2)使用串联缀合物实现了(-)-1-脱氧番茄碱的正式全合成。 手性配体控制芳基锂和烯酸酯的加成环化反应。 3)使用氨基膦-铑催化芳基硼烷试剂不对称加成到取代基上，以高立体选择性合成了5-芳基环己烯酮和反式-3,6-二取代环己酮，收率良好。 4)开发了手性氨基醇控制的炔基锌与硝基烯烃和醛的不对称加成。5)开发了手性恶唑啉配体控制的催化不对称分子内氢胺化。6)开发了手性氨基膦配体控制的二烷基锌与硝基烯烃的不对称加成。 7)使用由手性二醚配体控制的串联迈克尔加成烷基化方案实现了(+)-卤氯的正式合成。

项目成果

Chiral ligand-controlled asymmetric conjugate addition of lithium amides to enoates

• DOI: 10.1021/ja029633z
• 发表时间: 2003-03-12
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Doi, H;Sakai, T;Tomioka, K
• 通讯作者: Tomioka, K

Chiral Ligand-Controlled Asymmetric Conjugate Addition of a-Trimethylsilanylacetate to Acyclic and Cyclic Enones.

手性配体控制的α-三甲基硅烷基乙酸酯与无环和环状烯酮的不对称共轭加成。

• 发表时间: 2004
• 期刊: Chem.Pharm.Bull. 52(1)
• 作者: K.Yamada;T.Sakai;Ken-ichi Yamada;Takeo Sakai;富岡 清;Y.Yamamoto;T.Soeta;K.Yoshikai;K.Yoshikai;M.Yamashita;F.Valleix;M.Yamashita;Q.Chen;H.Fujieda;Yasutomo Yamamoto;Takahiro Soeta;Kazuya Yoshikai;Kazuya Yoshikai;Mitsuaki Yamashita;Fanny Vakkeux;Mitsuaki Yamashita;Qian Chen;Hiroki Fujieda;富岡 清;富岡 清;富岡 清;富岡 清;富岡 清;K.Tomioka;K.Tomioka;K.Tomioka;Y.Yamamoto;M.Iguchi;K.Yamada;M.Yamashita;T.Yasuhara;M.Yamashita;S.Hata;S.Hata;H.Doi;M.Kuriyama;T.Yasuhara;K.Yamada;T.Sakai;Yasutomo Yamamoto;Mayu Iguchi
• 通讯作者: Mayu Iguchi

Chiral ligand-controlled catalytic asymmetric epoxidation of unsaturated carbonyl compounds with peroxide.

手性配体控制的不饱和羰基化合物与过氧化物的催化不对称环氧化。

• 发表时间: 2003
• 期刊: Tetrahedron 59(25)
• 作者: K.Yamada;T.Sakai;Ken-ichi Yamada;Takeo Sakai;富岡 清;Y.Yamamoto;T.Soeta;K.Yoshikai;K.Yoshikai;M.Yamashita;F.Valleix;M.Yamashita;Q.Chen;H.Fujieda;Yasutomo Yamamoto;Takahiro Soeta;Kazuya Yoshikai;Kazuya Yoshikai;Mitsuaki Yamashita;Fanny Vakkeux;Mitsuaki Yamashita;Qian Chen;Hiroki Fujieda;富岡 清;富岡 清;富岡 清;富岡 清;富岡 清;K.Tomioka;K.Tomioka;K.Tomioka;Y.Yamamoto;M.Iguchi;K.Yamada;M.Yamashita;T.Yasuhara;M.Yamashita;S.Hata;S.Hata;H.Doi;M.Kuriyama;T.Yasuhara;K.Yamada;T.Sakai;Yasutomo Yamamoto;Mayu Iguchi;Ken-ichi Yamada;Mitsuaki Yamashita;Tomohisa Yasuhara;Mitsuaki Yamashita;Seiji Hata;Seiji Hata;Hirohisa Doi;Masami Kuriyama;Tomohisa Yasuhara;Ken-ichi Yamada;Takeo Sakai;Mitsuaki Yamashita;K.Tomioka;K.Tomioka;K.Tomioka;H.Doi;T.Yasuhara;K.Nishimura;A.Iida;K.Yamada;K.Konishi;Y.Tanaka
• 通讯作者: Y.Tanaka

K.Tomioka: "Molecular Assembly of C2-Symnietric Bis-(2S)-2-methyldodecanoyl-amides of a, w-Allylidenediamines into Coiled Coil and Twisted Ribbon Aggregates"J.Am.Chem.Soc.. 125・40. 12137-12142 (2003)

K. Tomioka：“α, w-烯丙二胺的 C2-对称双-(2S)-2-甲基十二烷酰基酰胺分子组装成卷曲线圈和扭曲带状聚集体”J.Am.Chem.Soc. 125・40。 -12142 (2003)

Chiral amino alcohol-mediated asymmetric conjugate addition of arylalkynes to nitroolefins.

• DOI: 10.1021/ol050643p
• 发表时间: 2005-05
• 期刊: Organic letters
• 影响因子: 5.2
• 作者: M. Yamashita;Ken‐ichi Yamada;K. Tomioka