Recently, the research team led by Prof. Weiping Liu and Assoc. Prof. Bolin Ji from the College of Chemistry, Chemical Engineering and Biotechnology at DHU has achieved a significant breakthrough in the field of earth-abundant-metal-catalyzed hydrogen-borrowing reactions. By employing an iron-based catalyst, the team successfully realized the enantioconvergent amination of secondary alcohols via a hydrogen-borrowing strategy, offering a novel approach to the synthesis of chiral amines. The results were recently published in Journal of the American Chemical Society under the title Iron-Catalyzed Enantioconvergent Amination of Alcohols.
Chiral amines are prevalent structural motifs in pharmaceuticals, agrochemicals, and natural products. Approximately 40~45% of small molecule pharmaceuticals, fine chemicals, and agrochemicals contain chiral amine fragments. The synthesis of chiral amines from inexpensive and readily available bulk chemicals via green and efficient approaches has attracted considerable attention. As simple, accessible, and environmentally benign feedstocks, alcohols have emerged as particularly attractive starting materials. The “hydrogen-borrowing” amination of alcohols offers distinct advantages, including step economy, redox neutrality, and the elimination of intermediate isolation and purification steps, making this methodology highly appealing to researchers.
Owing to the prevalence of chiral amines in natural products and pharmaceuticals, the research team developes an iron-catalyzed borrowing hydrogen enantioconvergent amination of alcohols in the presence of chiral phosphoric acid. This protocol effectively converts a range of secondary alcohols and amines, tolerating numerous functional groups, including hydroxyl, cyano, ester, and boronate groups, into chiral amines with high to excellent yields (up to 99%) and enantioselectivities (up to 99% ee). Notably, the compatibility with peptides, including di- and tripeptides, offers new possibilities for exploring chemical transformations in biological contexts.
The paper lists Sun Fan (2021 direct-entry Ph.D. candidate from the College of Chemistry, Chemical Engineering and Biotechnology at DHU) and Yao Boxuan (postgraduate student from Shantou University) as co-first authors, with Wang Siyi (2022 postgraduate student from DHU) serving as a co-author. Corresponding authors include Researcher Liu Weiping and Associate Professor Ji Bolin from DHU, along with Lecturer Ni Shaofei from Shantou University. DHU is designated as the primary corresponding institution.
Read the full paper: https://pubs.acs.org/doi/10.1021/jacs.5c07101
