Gold-Catalyzed Stereoselective Synthesis of Bicyclic Lactams and Ketones from N-Tosylynamidomethyl-Tethered Cyclohexenes

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• 作者：Chang-Zhi Zhong ; Po-Ting Tung ; Tsung-Han Chao ; Ming-Chang P. Yeh
• 刊名：Journal of Organic Chemistry
• 出版年：2017
• 出版时间：January 6, 2017
• 年：2017
• 卷：82
• 期：1
• 页码：481-501
• 全文大小：697K
• ISSN：1520-6904

文摘

Six-membered ring 3-enynamides underwent cycloisomerization in the presence of a catalytic amount of a gold(I) complex delivering mainly 4-azatricyclo[4.3.1.0^3,10]dec-2-ene derivatives and dibenz[cd,f]indole derivatives as the minor products under mild reaction conditions. Upon exposure to air, most aryl-substituted azatricycles led to bicyclic γ-lactams, while the ortho-tolyl- or alkyl-substituted azatricycles provided the corresponding bicyclic γ-lactams after oxidation with osmium tetraoxide and N-methylmorpholine-N-oxide. Under acidic conditions, the ortho-tolyl- or alkyl-substituted azatricycles were further transformed into 5-N-tosylaminomethyl-tethered bicyclo[4.2.0]octan-7-ones. The gold(I)-catalyzed tandem cycloisomerization/oxidation reaction also provided a new route for the synthesis of bridged bicyclic δ-lactams from six-membered ring 4-enynamides. The mild reaction conditions allowed the synthesis of a range of bicyclic γ- and δ-lactams and N-tosylaminomethyl-tethered bicyclo[4.2.0]octan-7-ones with high diastereoselectivities.