Ligand-Enabled β-C-H Arylation of α-Amino Acids Without Installing Exogenous Directing Groups.
Ligand-Enabled β-C-H Arylation of α-Amino Acids Without Installing Exogenous Directing Groups.
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DOI：
10.1002/anie.201610580
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发表时间：
2017-02-01
期刊：
影响因子：
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通讯作者：
Yu JQ
中科院分区：
文献类型：
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作者：
Chen G;Zhuang Z;Li GC;Saint-Denis TG;Hsiao Y;Joe CL;Yu JQ
在此，我们报告了由吡啶类配体实现的α-氨基酸的酸导向β-C（sp3）-H芳基化。该反应不需要安装外源导向基团，是可扩展的，并且能够在三个步骤中制备Fmoc保护的非天然氨基酸。吡啶类配体在这种新的C（sp3）-H芳基化的发展中至关重要。钯（II）催化的游离羧酸的α-氨基酸的β-C（sp3）-H芳基化反应已被吡啶或喹啉类配体所实现。芳基化是高度可扩展的，并且允许快速合成非天然氨基酸。还报道了碳环和其它脂肪酸的β-亚甲基C-H键。
Herein we report acid-directed β-C(sp3)–H arylation of α-amino acids enabled by pyridine-type ligands. This reaction does not require the installation of an exogenous directing group, is scalable, and enables the preparation of Fmoc-protected unnatural amino acids in three steps. The pyridine-type ligands are crucial in the development of this new C(sp3)–H arylation. The palladium(II)-catalyzed β-C(sp3)–H arylation of α-amino acids of free carboxylic acids enabled by pyridine or quinoline-based ligands has been developed. The arylation is highly scalable and allows for the rapid synthesis of non-natural amino acids. The β–methylene C–H bonds of carbocyclic rings and other aliphatic acids is also reported.