利用一價銠金屬催化劑催化具高鏡像選擇性之不對稱串聯合環反應

Abstract

本論文敘述以一價銠金屬及掌性雙環[2.2.1]雙烯配基L3b形成之催化劑，催化具有不同取代基的芳基硼酯化合物23與7-氮苯駢降冰片烯化合物26進行不對稱串聯合環反應，生成一系列具有茚烷(indane)結構的掌性環化產物27，共28個例子，最高產率達96%，以及高達99%的鏡像超越值。此反應在形成兩個新的碳-碳鍵的同時，亦可有效地建立三個連續的掌性中心。此外本論文亦探討以烯基硼試劑37與1,6烯炔起始物40進行不對稱串聯合環反應，合成一系列具有(diquinene)結構的掌性環化產物41，有 15 個例子，產率、鏡像超越值皆有良好的表現 (88% yield, 96% ee)。This thesis describes a highly enantioselective cascade cyclization of arylboronate esters 23 and 1,4-dihydro-1,4-iminonaphthalene 26 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 L3b. Under the optimal conditions, the annulated products 27 bearing an indane skeleton were generated in up to 96% yield and 99% ee as demonstrated in 28 examples featuring with three consecutive chiral centers. The second part of this thesis aims for studing enantioselective cascade cyclization reaction of 1,6-eynenes 40 and arylboronate esters 37. In the presence of rhodium(I)-catalyst in situ generated from L3f under optimal conditions, the annulated products 41 comprising a diquinene skeleton were produced in up to 88% yield and 96% ee, as demonstrated in 15 examples.