Development of Novel Carbanion Rearrangements as a Stereoselective Approach toward Heteroatom-containing Natural Products

新型碳负离子重排的开发作为含杂原子天然产物的立体选择性方法

• 批准号: 14350473
• 负责人: TOMOOKA Katsuhiko
• 金额: $ 9.54万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14350473/
• 关键词: carbanion; asymmetric synthesis; rearrangement; acetal; cyclic ether; pyrrole; 中員環エーテル; 芳香族アミン; ピリジン; アミノケトン; オキセタン; Stevens転位; カルベン; 環拡大; ビニルエーテル; aza-Wittig転位

The following novel carbanion reactions of hetero-functionalized system have been developed.I.Oxy systema)Ring-enlarging [2,3]-Wittig rearrangement of cyclic acetals : Stereoselective approach to medium-sized cyclic vinyl ethers.b)Ring-contracting [1,2]-Wittig rearrangement of cyclic acetals : Stereoselective approach to medium-sized cyclic ethers.c)Anionic ring-contraction reaction of cyclic acetal system : Stereoselective approach to multi-functionalized oxetanes.d)[1,4]-Wittig rearrangement containing ethynylvinylmethanol-derived migration terminus : Tandem rearrangement-aldol reaction.II.Aza systema)Ring-enlarging aza-[1,2] and [2,3]-rearrangement of cyclic hemiaminals.b)Asymmetric aza-Wirtig rearrangement induced by Sn-Li transmetalation.c)The sequential carbanion reactions of phthalimide-derived alkynyl hemiaminal: Efficient approach to polysubstituted pyrrole via four components coupling.d)Stevens rearrangement of a cyclic hemiacetal system: Diastereoselective approach to chiral α-amino ketone.

下列新的异官能团化体系的碳负离子反应已被开发出来。I.氧合体系)环缩醛的扩环[2，3]-Wittig重排：中等尺寸的环乙烯醚的立体选择性方法。b)环缩醛的环收缩[1，2]-Wittig重排：中型环醚的立体选择性方法。c)环缩醛体系的阴离子环-收缩反应：多官能化氧烷的立体选择性方法d)[1，4]-Wittig重排含乙炔基乙烯基甲醇衍生的迁移终点：串联重排-Aldol反应。和[2，3]-环半胺的重排。b)由锡-锂易位引起的不对称氮杂-Wirtig重排。c)邻苯二甲酰亚胺衍生的炔半胺的顺序碳负离子反应：通过四组分偶联得到多取代吡咯的有效方法。d)环半缩醛体系的史蒂文斯重排：手性α-氨基酮的非对映选择性方法。

项目成果

K.Tomooka, M.Ito 他: "Main Group Metals in Organic Synthesis"Wiley, Weinheim. 905 (2004)

K. Tomooka、M. Ito 等人：“有机合成中的主族金属”Wiley，Weinheim 905 (2004)。

David Hodgson, 友岡克彦: "Enantioselective Synthesis by Lithiation Adjacent to O and Subsequent Rearrangement in Topics in Organometallic Chemistry"Springer-Uerlag. (2003)

David Hodgson、Katsuhiko Tomooka：“有机金属化学主题中邻接 O 的锂化和后续重排的对映选择性合成”Springer-Uerlag (2003)。

Main group metals in organic synthesis

• 发表时间: 2004
• 作者: 山本 尚;大嶌 幸一郎

The Chemistry of Organolithium Compound

有机锂化合物的化学

• 发表时间: 2004
• 作者: T. Kirimura;et al.;K.Tomooka 他
• 通讯作者: K.Tomooka 他

D.M.Hodgson, K.Tomooka, E.Gras: "Enantioselective Synthesis by Lithiation Adjacent to Oxygen and Subsequent Rearrangement"Top.Organomet.Chem.. 5. 217-250 (2003)

D.M.Hodgson、K.Tomooka、E.Gras：“通过与氧相邻的锂化和随后的重排进行对映选择性合成”Top.Organomet.Chem.. 5. 217-250 (2003)