Zhang Biao, Ruan Junhao, Seidel Daniel, Chen Weijie
School of Chemical Science and Engineering, Institute for Advanced Studies, Tongji University, 1239 Siping Rd, Shanghai, 200092, P. R. of China.
Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, Gainesville, FL 32611, USA.
Angew Chem Int Ed Engl. 2023 Sep 4;62(36):e202307638. doi: 10.1002/anie.202307638. Epub 2023 Jul 28.
Unprotected cis-2,3-diarylpiperidines are synthesized through an unprecedented palladium-catalyzed cross-coupling reaction between aryl halides and elusive endocyclic 1-azaallyl anions. These intermediates are generated in situ by the deprotonation of 2-aryl-1-piperideines, precursors that are readily prepared in two operations from simple piperidines. An asymmetric version of this reaction with (2R, 3R)-iPr-BI-DIME as the ligand provides products in moderate to good yields and enantioselectivities. This study significantly expands the synthetic utility of endocyclic 1-azaallyl anions.
未受保护的顺式-2,3-二芳基哌啶是通过芳基卤化物与难以捉摸的内环状1-氮杂烯丙基阴离子之间前所未有的钯催化交叉偶联反应合成的。这些中间体是通过2-芳基-1-哌啶的去质子化原位生成的，2-芳基-1-哌啶是由简单哌啶通过两步操作容易制备的前体。以(2R, 3R)-异丙基-BI-DIME作为配体的该反应的不对称版本，以中等至良好的产率和对映选择性提供产物。这项研究显著扩展了内环状1-氮杂烯丙基阴离子的合成效用。
