Highly Diastereoselective Arylations of Substituted Piperidines

详细信息    查看全文

• 作者：Stephanie Seel ; Tobias Thaler ; Keishi Takatsu ; Cong Zhang ; Hendrik Zipse ; Bernd F. Straub ; Peter Mayer ; Paul Knochel
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：April 6, 2011
• 年：2011
• 卷：133
• 期：13
• 页码：4774-4777
• 全文大小：822K
• 年卷期：v.133,no.13(April 6, 2011)
• ISSN：1520-5126

文摘

A highly diastereoselective methodology for the preparation of various substituted piperidines via Negishi cross-couplings with (hetero)aryl iodides was developed. Depending on the position of the C鈭抁n bond relative to the nitrogen (position 2 vs position 4), the stereoselectivity of the coupling can be directed toward either the trans- or cis-2,4-disubstituted products. Density functional theory calculations on the relative stabilities of the Zn and Pd intermediates were performed to explain the high diastereoselectivities obtained. A novel 1,2-migration of Pd further expands this method to the stereoselective preparation of 5-aryl-2,5-disubstituted piperidines.