一價銠金屬催化芳香基硼酯與降冰片烯衍生物進行不對稱串聯合環反應

Abstract

本論文敘述利用一價銠金屬及掌性雙環[2.2.1]雙烯配基L12i所形成之催化劑，催化不同芳基硼酯59與降冰片烯(norbornene)衍生物37進行不對稱合環反應，得到一系列具有茚烷(indane)結構之掌性環化產物60，產率為13–>99%，鏡像超越值為12–99%。此反應的驅動力為環張力能量之釋放，不僅建立了兩個新的碳-碳鍵，也同時生成三個連續的立體中心。此外，本文也探討了具有張力之雙鍵與在烯丙位具有離去基之雙鍵兩者的反應性差異。

An enantioselective tandem annulation of norbornene derivatives 37 with arylboronic esters 59 is reported. In the presence of 3.0 mol % of Rh(I)-catalyst, which is in situ generated from the [RhCl(C2H4)2]2 and the chiral bicyclo[2.2.1]heptadiene ligand L12i, the desired chiral indanes 60 are obtained in 13–>99% yields with 12–99% ees. This asymmetric transformation, which is triggered by the release of ring strain, not only forms two carbon-carbon bonds, but establishes three consecutive new chiral centers. Furthermore, in this thesis, we also discuss the reactivity difference between the strain olefins and the double bonds with leaving groups at allylic position.