銠金屬催化脂肪族醛亞胺不對稱烯丙基化反應

Rh-catalyzed Asymmetric Allylation of Aliphatic Imines

李韋賢(Wei-Sian Li) ； 吳學亮(Hsyueh-Liang Wu)

《化學》 78卷3期 (2020/09) Pp. 191-197

https://doi.org/10.6623/chem.202009_78(3).006

摘要

以3.0mol％之一價銠金屬與掌性雙環[2.2.1]雙烯配體L1a形成之催化劑，於加入兩當量水之反應條件下，催化烯丙基三氟硼酸鉀鹽7與脂肪族醛亞胺6進行不對稱加成反應。加成產物生成產率為21－95％，鏡像選擇性為85－98％。利用此方法產生的掌性加成產物8n與8o經由多步反應後可以合成天然生物鹼(S)-Coniine．HCl，(R)-Coniceine．HCl，(−)-Indolizidine 167B．HCl與(−)-Pelletierine。

關鍵字

一價銠金屬催化 ； 脂肪族醛亞胺 ； 烯丙基反應

並列摘要

An enantioselective allylation of aliphatic aldimines was developed, in the presence of 3.0 mol % of an Rh(I)-catalyst in situ generated from the [RhCl(C_2H_4)_2]_2 and chiral bicyclo[2.2.1] heptadiene ligand L1a, to afford the corresponding chiral homoallylic amines bearing an α- aliphatic side chain in 21-95% yields with 85-98% ee's under aqueous reaction conditions. Total syntheses of (R)-coniceine, (-)-Indolizidine 167B, (S)-Coniine and (-)-Pelletierine alkaloids were carried out to demonstrate the synthetic usefulness of this method.

並列關鍵字

Rh(I)-catalyst ； Aliphatic aldimines ； Enantioselective allylation