Yu Longhui, Nagata Yuuya, Nakamura Hugh
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong 999077, China.
WPI Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo 001-0021, Japan.
J Am Chem Soc. 2024 Jan 31;146(4):2549-2555. doi: 10.1021/jacs.3c11016. Epub 2024 Jan 19.
A short, atroposelective synthesis of cihunamide B () is reported. The feature of this report is the decagram-scale SAr reaction of l-tryptophan derivatives, followed by atroposelective Larock macrocyclization. This strategy allowed the construction of a Trp-Trp cross-linkage with unprecedented atropisomerism. The atroposelectivity of this Larock macrocyclization has been investigated through a combination of experimental and computational chemistry, yielding detailed insights into the synthesis of biaryl linkages. It also enabled the concise synthesis of cihunamide B (), which is expected to be a potential antibacterial agent.
报道了西胡酰胺B（）的一种简短、对映选择性合成方法。本报道的特点是L-色氨酸衍生物的十克规模的亲核芳香取代反应（SAr反应），随后进行对映选择性的拉罗克大环化反应。该策略实现了具有前所未有的阻转异构现象的色氨酸-色氨酸交联结构的构建。通过实验化学和计算化学相结合的方法研究了这种拉罗克大环化反应的对映选择性，为联芳基键的合成提供了详细的见解。它还实现了西胡酰胺B（）的简洁合成，该化合物有望成为一种潜在的抗菌剂。
