一價銠金屬催化具高鏡像選擇性之不對稱串聯反應：合成掌性二氫萘胺

Abstract

本論文敘述使用一價銠金屬與掌性雙環[2.2.1]雙烯配體L6a所形成的催化劑，催化𝛽-位具有不同取代基的酯化合物54與不同乙腈芳基硼酯24，進行不對稱串聯合環反應。在最優化條件下，生成一系列具有二氫萘胺結構之環化產物55，共有29個例子，具有最高79%的產率與高達99%的鏡像超越值。此外，以鈀金屬對乙醯基產物58aa的亞胺雙鍵進行氫化反應，可生成具有連續三個掌性中心的產物71，產率、鏡像超越值以及非鏡像異構物比例皆有良好的表現(95% yield, 96% ee, d.r.> 20:1)。This thesis describes a highly enantioselective cascade cyclization of 𝛽-substituted ester 54 and arylboronate esters 24 in the presence of a rhodium(I)-catalyst prepared in situ from [RhCl(C2H4)2]2 and the chiral bicyclo[2.2.1]heptadiene ligand L6a. Under the optimal conditions, the annulated products 55 with a dihydronaphthalenamine skeleton were generated in up to 79% yield and 99% ee demonstrated in 29 examples. Further hydrogenation of 58aa generated product 71 with three chiral centers in good yield, enantioselectivity value, and diastereomer ratio (95% yield, 96% ee, d.r.> 20:1).