A simple copper-promoted one-pot Sandmeyer trifluoromethylation of aromatic amines with Langlois＇ reagent has been demonstrated. The reaction is performed in mild reaction conditions under an air atmosphere with good...A simple copper-promoted one-pot Sandmeyer trifluoromethylation of aromatic amines with Langlois＇ reagent has been demonstrated. The reaction is performed in mild reaction conditions under an air atmosphere with good substrate scope and functional group compatibility. It provides an alternative and straightforward synthetic approach to access a variety of trifluoromethylated arenes.展开更多
Aromatics have a broad application in our everyday life ranging from plastics, coatings and fibres, to food and pharmaceuticals. To date the bulk of these aromatics is derived from naphtha-based pet-rochemistry. Howev...Aromatics have a broad application in our everyday life ranging from plastics, coatings and fibres, to food and pharmaceuticals. To date the bulk of these aromatics is derived from naphtha-based pet-rochemistry. However, recent progress in the fermentative production of metabolites using renew-able resources and engineered microbes has enabled the production of bio-precursors, such as 4-amino benzoic acid (pABA) and 2-amino benzoic acid (oABA). In this work we explored the feasibility of Sandmeyer reactions for the conversion of pABA to terephthalic and oABA salicylic acid, providing two very important platform chemicals for the chemical and pharmaceutical industries. We could demonstrate that both acids can be obtained from the amino benzoic acids derived from the shikimate pathway in microbes and plants. Good conversions could be achieved using Sandmeyer reactions at mild conditions with biodegradable reagents and without organic solvents.展开更多
BAY-069是目前体外活性最强的支链氨基酸转氨酶1(BCAT1)抑制剂,但其报道的合成路线存在原料成本较高、总收率极低和中间体结构表征不充分等缺点。本研究基于已有合成路线,重点对其合成工艺中的Ullmann偶联反应进行了系统优化。以1-硝基...BAY-069是目前体外活性最强的支链氨基酸转氨酶1(BCAT1)抑制剂,但其报道的合成路线存在原料成本较高、总收率极低和中间体结构表征不充分等缺点。本研究基于已有合成路线,重点对其合成工艺中的Ullmann偶联反应进行了系统优化。以1-硝基萘(1)为起始原料,经过7步反应和手性色谱柱手性拆分合成目标化合物BAY-069。所有中间体和目标化合物均经1 H NMR,13 C NMR和HR-MS表征。以Ullmann偶联反应为主要优化步骤的路线,其优化后的总收率为11.0%(3b→(±)-BAY-069),是原总收率1.6%(3a→(±)-BAY-069)的6.9倍。展开更多
基金We acknowledge the financial support for this work from the National Natural Science Foundation of China （Nos. 21502070 and 21562041） and the Fundamental Research Funds for the Central Universities （No. JUSRP51626B）.
文摘A simple copper-promoted one-pot Sandmeyer trifluoromethylation of aromatic amines with Langlois＇ reagent has been demonstrated. The reaction is performed in mild reaction conditions under an air atmosphere with good substrate scope and functional group compatibility. It provides an alternative and straightforward synthetic approach to access a variety of trifluoromethylated arenes.
文摘Aromatics have a broad application in our everyday life ranging from plastics, coatings and fibres, to food and pharmaceuticals. To date the bulk of these aromatics is derived from naphtha-based pet-rochemistry. However, recent progress in the fermentative production of metabolites using renew-able resources and engineered microbes has enabled the production of bio-precursors, such as 4-amino benzoic acid (pABA) and 2-amino benzoic acid (oABA). In this work we explored the feasibility of Sandmeyer reactions for the conversion of pABA to terephthalic and oABA salicylic acid, providing two very important platform chemicals for the chemical and pharmaceutical industries. We could demonstrate that both acids can be obtained from the amino benzoic acids derived from the shikimate pathway in microbes and plants. Good conversions could be achieved using Sandmeyer reactions at mild conditions with biodegradable reagents and without organic solvents.
文摘BAY-069是目前体外活性最强的支链氨基酸转氨酶1(BCAT1)抑制剂,但其报道的合成路线存在原料成本较高、总收率极低和中间体结构表征不充分等缺点。本研究基于已有合成路线,重点对其合成工艺中的Ullmann偶联反应进行了系统优化。以1-硝基萘(1)为起始原料,经过7步反应和手性色谱柱手性拆分合成目标化合物BAY-069。所有中间体和目标化合物均经1 H NMR,13 C NMR和HR-MS表征。以Ullmann偶联反应为主要优化步骤的路线,其优化后的总收率为11.0%(3b→(±)-BAY-069),是原总收率1.6%(3a→(±)-BAY-069)的6.9倍。
