一價銠金屬催化具鏡像選擇性串聯環化：以配體效應控制銠金屬1,2-重排合成掌性2-茚酮

Abstract

本論文敘述利用一價銠金屬與軸掌性雙膦配體(S)-BINAP (L1) 所形成之催化劑，催化不同的芳基硼酯34與反丁烯二酸二酯化合物32進行不對稱的串聯環化反應，獲得一系列具有2-茚酮(2-indanone)結構之掌性化合物35，共有19個例子，產率最高達93%，鏡像選擇性則是最高達89% ee，且改使用順丁烯二酸二甲酯(32b’)進行反應時，結果與反丁烯二酸二甲酯(32b)相同，並透過推測之反應機構證明其可能原因。在催化循環中的關鍵步驟為1,2-銠金屬轉移(1,2-rhodium shift)反應，透過氘標記反應實驗證明得到的產物35是經由1,2-銠金屬轉移反應。

This thesis describes an enantioselective tandem cyclization of fumarate diesters 32 with various arylboronic esters 34. In the presence of 5.0 mol% of Rh(I)-catalyst in situ generated from the [RhCl(cod)]2 and the axially chiral bisphosphine ligand (S)-BINAP ((S)-L1), the desired chiral 2-indanone derivatives 35 are obtained in up to 93% yield and 89% ee demonstiated in 19 examples. When substituting dimethyl maleate with dimethyl fumarate, we yielded the comparable result to the fumarate. And the possible reason was substantiated through the inferred reaction mechanism. Furthermore, the key step of catalytic cycle is 1,2-rhodium shift, deuterium labeling experiments were conducted to provide a solid evidence of 1,2-rhodium shift, leading to the formation of 35.