Reiersølmoen Ann Christin, Solvi Thomas N, Fiksdahl Anne
Department of Chemistry, Norwegian University of Science and Technology, Høgskoleringen 5, 7491, Trondheim, Norway.
Beilstein J Org Chem. 2021 Jan 19;17:186-192. doi: 10.3762/bjoc.17.18. eCollection 2021.
Chiral cyclam (1,4,8,11-tetraazacyclotetradecane) derivatives were synthesized stepwise from chiral mono-Boc-1,2-diamines and (dialkyl)malonyl dichloride via open diamide-bis(Boc-amino) intermediates (65-91%). Deprotection and ring closure with a second malonyl unit afforded the cyclam tetraamide precursors (80-95%). The new protocol allowed the preparation of the target cyclam derivatives (53-59%) by a final optimized hydride reduction. Both the open tetraamine intermediates and the cyclam derivatives successfully coordinated with AuCl to give moderate to excellent yields (50-96%) of the corresponding novel tetra-coordinated -Au(III) complexes with alternating five- and six-membered chelate rings. The testing of the catalytic ability of the cyclam-based -Au(III) complexes demonstrated high catalytic activity of some complexes in selected test reactions (full conversion in 1-24 h, 62-97% product yields).
手性环胺（1,4,8,11-四氮杂环十四烷）衍生物通过手性单-Boc-1,2-二胺和（二烷基）丙二酰二氯，经开放的二酰胺-双（Boc-氨基）中间体逐步合成（产率65-91%）。用第二个丙二酰单元进行脱保护和闭环反应得到环胺四酰胺前体（产率80-95%）。新方法通过最终优化的氢化物还原反应制备目标环胺衍生物（产率53-59%）。开放的四胺中间体和环胺衍生物均成功与AuCl配位，得到相应的具有交替五元环和六元螯合环的新型四配位-Au(III)配合物，产率适中至优异（50-96%）。基于环胺的-Au(III)配合物的催化能力测试表明，某些配合物在选定的测试反应中具有高催化活性（1-24小时内完全转化，产物产率62-97%）。
