（一）鈀與酸催化的分子內連續反應－雜環化合物的合成（二）紅藻氨酸差向異構體前驅物之合成

Abstract

本文共有三個主題，分別為探討鈀金屬催化的連續環化反應合成環戊[b]吲哚；路易斯酸或布忍斯特酸的催化反應合成螺旋及雜環化合物以及紅藻氨酸差向異構體前驅物之合成。 （1）利用鈀（II）催化帶有環型共軛烯酮之炔基苯胺衍生物進行連續環化反應，可以成功合成具有環戊[b]吲哚之骨架化合物。鈀（II）催化劑先與炔基進行配位形成鈀（II）錯合物。三氟甲磺醯胺攻擊鈀－炔中間體，形成3-鈀吲哚中間體。碳－鈀鍵進行分子內Michael加成反應得到環戊[b]吲哚化合物。其中PdCl2(PhCN)2和極性溶劑N,N-二甲基甲醯胺（DMF）在這個反應中扮演重要角色。 （2）利用TfOH催化帶有環型2,3-環氧基-5-磺醯胺-7-炔-8-芳香環-1-醇之衍生物進行連續環化反應，反應先行semipinacol重排接著經由炔－醛複分解反應，得到含氮螺旋化合物－7-氮螺旋[4.5]癸烷。利用三氯化鐵或PPh3AuCl/AgOTf共催化系統與含有環氧炔醇基化合物進行反應，成功得到八氫異喹啉產物。另外，環己酮上有甲基取代，環氧乙烷會經由不同semipinacol重排路徑，最後得到吡咯或呋喃產物。 （3）Kainoid類天然物已被報導具有多樣化的生物活性，所以發展快速且有效率的方法來合成吡咯啶衍生物是相當重要的。本章主旨在利用PPh3AuCl/AgOTf共催化系統對含氮的烯炔醇化合物進行分子內克萊森類型重排反應，合成順式2,3,4-三取代紅藻氨酸前驅物之差向異構物。

This dissertation contains three topics. The first part is the synthesis of cyclopenta[b]indoles via the palladium(II)-catalyzed cascade reaction of alkynylanilines bearing a tethered cyclic enones. The second part is the synthesis of 7-azaspiro[4.5]decanes or spiro[4.4]nonanes via the TfOH-catalyz- ed tandem semipinacol rearrangement, followed by alkyne-aldehyde metathesis. Finally, the synthesis of the C-2 epimer of kainoic acid is described. (1) The Pd(II)-catalyzed tandem intramolecular cyclization reaction of alkynylanilines bearing a tethered cyclic enones afforded the cyclopenta[b]indole derivatives. Firstly, the Pd(II) catalyst coordinated to alkyne to form a Pd-alkyne complex. Then attack of the tosylamide onto the Pd-alkyne moiety took place to give a palladiated indole. The resulting arylpalladium underwent an intramolecular Michael addition to the pendant conjugate enones to provide the cyclopenta[b]indole derivatives. Both the catalyst PdCl2(PhCN)2 and the solvent DMF are critical for the reaction. (2) A TfOH-catalyzed tandem reaction of 2,3-epoxy-5-aza-5-tosyl-7-yn-8- aryl-1-ols is reported. The reaction undergoes a tandem semipinacol rearrangement/alkyne-aldehyde metathesis to afford azaspirocyclic or spirocyclic derivatives. The C-2 arylpropargylsulfonamide-tethered 2,3-epoxy- cyclohexan-1-ones react with Lewis acid, such as FeCl3 or PPh3AuCl/AgOTf to produce 8H-hydroisoquinolines. Substrates bearing a geminal dimethyl group at C-5 and methyl group at C-3 of the ring can be utilized to afford pyrrole or furan derivatives using a catalytic amount of Lewis acid. (3) PPh3AuCl/AgOTf catalyzed intramolecular Claisen rearrangement of (Z)-enynol was developed to provide cis-3-acyl-4-alkenylpyrrolidines containing an oxazoline ring, which are the precursor of the C-2 epimers of kainoic acids.