Asymmetric Organic Synthesis Via New Enantioenriched Allylsilanes

通过新型对映体富集的烯丙基硅烷进行不对称有机合成

• 批准号: 11650873
• 负责人: SUGINOME Michinori
• 金额: $ 2.11万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650873/
• 关键词: Asymmetric Synthesis; Allylsilane; Bis-silylation; Cyclization; Stereoselectivity; Lewis Acid; Chirality Transfer; Palladium Catalyst; シクロアルケン; 光学活性アリルシラン; テトラヒドロフラン; オキセパン; アルデヒド; 不斉転写

Highly enantioenriched allylsilanes bearing an ω-hydroxy group were synthesized stereoselectively via a sequence involving palladiumcatalyzed intramolecular bis-silylation of allylic alcohols. The new functionalized allylsilanes reacted with aldehydes in the presence of Lewis acids, giving cyclic ethers via acetalization followed by intramolecular Hosomi-Sakurai reaction. The allylsilanes with an ω-hydroxy group on their γ-alkyl group afforded 2-substituted cyclic ethers with 3-(1-alkenyl) group stereoselectively. For instance, reactions of (S)-(E)-6-(dimethylphenylsilyl) dec-4-en-1-ol (93% ee) and (R)-(E)-7-(dimethylphenylsilyl) undec-5-en-1-ol (96% ee) with heptanal afforded trans-2-hexyl-3-((E)- 1-hexenyl) tetrahydropyran (92% ee) and trans-2-hexyl-3-((E)-1-hexenyl) oxepane (94% ee), respectively, in good yields with >97% stereoconservation. On the other hand, allylsilanes with an ω-hydroxy group on their α-alkyl chain afforded 2, 3-disubstituted oxacycloalk-4-enes stereoselectively. In these reactions, not only high diastereoselectivity but also highly stereoselective transfer of chirality from the allylsilanes to the cyclic ethers was accomplished.

通过钯催化的烯丙醇分子内双硅烷化反应，立体选择性地合成了高对映体富集的含ω-羟基的烯丙基硅烷。在刘易斯酸存在下，新型功能化烯丙基硅烷与醛反应，通过缩醛化和分子内Hosomi-Sakurai反应生成环醚。γ-烷基上带有ω-羟基的烯丙基硅烷立体选择性地合成了3-（1-烯基）-2-取代环醚。例如，（S）-（E）-6-甲基-IH-吡唑的反应是优选的。（二甲基苯基甲硅烷基）癸-4-烯-1-醇（93%ee）和（R）-（E）-7-（二甲基苯基甲硅烷基）癸-4-烯-1-醇（93%ee）。（二甲基苯基甲硅烷基）十一碳-5-烯-1-醇（96%ee）与庚醛反应分别得到反式-2-己基-3-（（E）-1-己烯基）四氢吡喃（92%ee）和反式-2-己基-3-（（E）-1-己烯基）氧杂环庚烷（94%ee），产率良好，立体保守性>97%。而α-烷基链上带有ω-羟基的烯丙基硅烷则立体选择性地合成了2，3-二取代氧杂环烷烃-4-烯。在这些反应中，不仅实现了高非对映选择性，而且实现了手性从烯丙基硅烷到环醚的高度立体选择性转移。

项目成果

Michinori Suginome: "Asymmetric Synthesis of 2, 3-Disubstituted Oxepanes via Acetalization-Cyclization of an Enantioenriched Functionalized Allylsilane with Aldehydes"Chem.Commun (Cambridge). 2537-2538 (1999)

Michinori Suginome：“通过对映体富集的官能化烯丙基硅烷与醛的缩醛化-环化来不对称合成 2, 3-二取代的氧杂环己烷”Chem.Commun（剑桥）。

SUGINOME,Michinori: "Solid-Phase Synthesis and Asymmetric Reactions of Polymer-Supported Highly Enantioenriched Allylsilanes"J.Am.Chem.Soc.. (印刷中). (2001)

SUGINOME, Michinori：“聚合物支持的高度对映烯丙基硅烷的固相合成和不对称反应”J.Am.Chem.Soc.（出版中）。

Michinori Suginome: "Asymmetric Synthesis of Cyclic alkenes via Cyclization of Enantioenriched Allylsilanes"Synlett. in press. (2001)

Michinori Suginome：“通过对映体富集的烯丙基硅烷的环化来不对称合成环烯烃”Synlett。

SUGINOME,Michinori: "Asymmetric Synthesis of Cyclic Alkenes via Cyclization of Enantioenriched Allylsilanes"Synlett. (印刷中). (2001)

SUGINOME，Michinori：“通过对映体富集的烯丙基硅烷的环化来不对称合成环状烯烃”Synlett（出版中）。

M.Suginome: "Asymmetric Synthesis of 2,3-Disubstituted Oxepanes via Acetalization-cyclization of an Enantioenriched Allylsilane with Aldehydes"Chemical Communication(Cambridge). 2537-2538 (1999)

M.Suginome：“通过对映体富集的烯丙基硅烷与醛的缩醛化-环化来不对称合成2,3-二取代的氧杂环己烷”《化学通讯》（剑桥）。