Koshizuka Masayoshi, Takahashi Naoya, Shimada Naoyuki
Laboratory of Organic Chemistry for Drug Development and Medical Research Laboratories, Department of Pharmaceutical Sciences, Kitasato University, 5-9-1 Shirokane, Minatao-ku, Tokyo 108-8641, Japan.
Laboratory of Organic Chemistry for Molecular Transformations, Department of Chemistry and the Institute of Natural Sciences, Nihon University, 3-25-40 Sakurajosui, Setagaya-ku, Tokyo 156-8550, Japan.
Chem Commun (Camb). 2024 Oct 3;60(80):11202-11222. doi: 10.1039/d4cc02994a.
Amides and peptides are ubiquitous functional groups found in several natural and artificial materials, and they are essential for the advancement of life and material sciences. In particular, their relevance in clinical medicine and drug discovery has increased in recent years. Dehydrative condensation of readily available carboxylic acids with amines is the most "direct" method for amide synthesis; however, this methodology generally requires a stoichiometric amount of condensation agent (coupling reagent). Catalytic direct dehydrative amidation has become an "ideal" methodology for synthesizing amides from the perspective of green chemistry, with water as the only byproduct in principle, high atom efficiency, environmentally friendly, energy saving, and safety. Conversely, organoboron compounds, such as boronic acids, which are widely used in various industries as coupling reagents for Suzuki-Miyaura cross-coupling reactions or pharmaceutical structures, are environmentally friendly molecules that have low toxicity and are easy to handle. Based on the chemical properties of organoboron compounds, they have potential Lewis acidity and the ability to form reversible covalent bonds with dehydration, making them attractive as catalysts. This review explores studies on the development of direct dehydrative amide/peptide bond formation reactions from carboxylic acids using organoboron catalysis, classifying them based on chemical bonding and catalysis over approximately 25 years, from the early developmental days to 2023.
酰胺和肽是在多种天然和人工材料中普遍存在的官能团，它们对于生命科学和材料科学的发展至关重要。特别是，近年来它们在临床医学和药物发现中的相关性有所增加。将容易获得的羧酸与胺进行脱水缩合是酰胺合成最“直接”的方法；然而，这种方法通常需要化学计量的缩合剂（偶联试剂）。从绿色化学的角度来看，催化直接脱水酰胺化已成为一种“理想”的酰胺合成方法，原则上以水作为唯一的副产物，具有高原子效率、环境友好、节能和安全等优点。相反，有机硼化合物，如硼酸，作为铃木-宫浦交叉偶联反应的偶联试剂或药物结构，在各个行业中广泛使用，它们是低毒且易于处理的环境友好型分子。基于有机硼化合物的化学性质，它们具有潜在的路易斯酸性以及与脱水形成可逆共价键的能力，使其作为催化剂具有吸引力。本综述探讨了使用有机硼催化从羧酸直接脱水形成酰胺/肽键反应的发展研究，根据化学键合和催化作用，对从早期发展阶段到2023年大约25年的研究进行了分类。
