利用有機雙關能不對稱催化劑進行Vinylogous Michael Addition/Henry Reaction Cascade 合成四氫芴酮衍生物

Organocatalytic Enanotioselective Synthesis of Tetrahydrofluoren-9-9ones via Vinylogous Michael Addition/Henry Reaction Cascade of 1,3-Indandion-Derived Pronucleophiles

張耕華(Chang Geng-Hua)

指導教授 ： 林文偉

國立臺灣師範大學/理學院/化學系/碩士(2016年)

https://doi.org/10.6345/NTNU202204358

摘要

本論文主要為開發新穎1,3-茚二酮衍生物為親核性前驅物與不同親電
子試劑的反應在有機雙功能金雞納鹼衍生物催化下，藉由Vinylogous
Michael/Henery Reaction Cascade 建構四氫芴酮衍生物。

第一部分，利用1,3-茚二酮衍生物和(E)-(2-硝基乙烯基)苯的有機不對稱催化反應，可建構具四個立體中心包含一個四級碳的多取代四氫芴酮衍生物；反應結果得單一非鏡像異構物，產率為43-98%，鏡像超越值可高達98%；同時，探討此類親性試劑運用在多取代親電子性試劑，像是(Z)-叔丁基3-(2-乙氧基-2-氧代亞乙基)-2- oxoindoline-1-羧酸上的應用，可套用上述的研究概念生成四氫螺[芴-4,3'-二氫吲哚]-1',3-二羧酸衍生物，有高達98% 的產率及83% 的鏡像超越值。

第二部分，使用具有多取代羰基香豆素衍生物及不同取代之亞胺衍生
物，經由[3+2] 反應，合成出具有多個掌性中心的苯並吡喃並[3,4-c]吡咯烷衍生物，不僅有良好的產率、非鏡像異構比及高達 99% 的鏡像超越值，同時，預期外的分子內官能團轉移，也為我們詳細探討之。

關鍵字

有機不對稱催化

並列摘要

Bifunctional organocatalyst dominated for asymmetric catalysis via utilizing novel
1,3-indandionederived pronucleophiles with wide variety of nitoalkenes for
Vinylogous Michael addition/Henry cyclization cascade to generate tetrahydrofluoren-
9-ones derivatives with excellent result.

Part I: An unprecedented organocatalytic enantioselective vinylogous Michael
addition/Henry cyclization cascade is presented for the synthesis of highly substituted
tetrahydrofluoren-9-ones employing novel 1,3-indandionederived pronucleophiles
94 and nitroalkenes. Following a very simple protocol, a wide range of products
were obtained in good to excellent yields and with excellent enantioinduction
(43−98% yield, up to 98% ee). The reaction proceeded with excellent diastereocontrol
despite the simultaneous generation of four stereogenic centers. Surprisingly, when 2-
(1- phenylethylidene)-1H-indandione 94h-i was used as a pronucleophile, no
cyclization was observed, and only Michael addition adducts 98 were furnished in
very good yields and excellent enantioselectivities.

Part II: An enantioselective synthesis of benzopyrano[3,4-c]pyrrolidine derivatives via
organocatalyzed [3+2] cycloaddition has been achieved. Cinchona alkaloid-derived
organocatalysts as Bronsted bases have been examined for this asymmetric
cycloaddition of o-hydroxy aromatic aldimines with 3-substituted coumarins.
An unexpected rearrangement of the quaternary acyl moiety in the products resulted
in an in situ protection of the o-hydroxy group.

並列關鍵字

Vinylogous

參考文獻

參考資料

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