Gold(I)/(III)-catalyzed synthesis of 2-substituted piperidines; valency-controlled cyclization modes

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• 作者：Nobuyoshi Morita ; ^{morita@ac.shoyaku.ac.jp" class="auth_mail" title="E-mail the corresponding author} ; Tomonori Tsunokake ; Yuji Narikiyo ; Mayuka Harada ; Tatsuyuki Tachibana ; Yuta Saito ; Shintaro Ban ; Yoshimitsu Hashimoto ; Iwao Okamoto ; Osamu Tamura ; ^{tamura@ac.shoyaku.ac.jp" class="auth_mail" title="E-mail the corresponding author}
• 关键词：Oxophilic gold(III) catalyst ; 蟺-Philic gold(I) catalyst ; Cyclization ; Meyer&ndash ; Schuster rearrangement ; Aza-Michael addition
• 刊名：Tetrahedron Letters
• 出版年：2015
• 出版时间：4 November 2015
• 年：2015
• 卷：56
• 期：45
• 页码：6269-6272
• 全文大小：919 K

文摘

Strategic use of hard gold(III) and soft gold(I) catalysts provides facile access to two types of 2-substituted piperidines from propargylic alcohols. Thus, heating propargylic alcohols in the presence of AuBr₃ results in cyclization to furnish piperidines having an acetylenic moiety, due to activation of the propargylic hydroxyl group by coordination of gold(III). On the other hand, the catalyst [Ph₃PAuNTf₂]₂PhMe induces Meyer–Schuster rearrangement of propargylic alcohols to give 伪,尾-unsaturated ketones, which undergo intramolecular aza-Michael addition to afford piperidines bearing a carbonyl group, due to activation of the triple bond by coordination of gold(I).