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铜催化的不对称 C(sp 2 )-H 芳基化反应合成 P 和轴向手性磷化合物。

Copper-catalyzed asymmetric C(sp)-H arylation for the synthesis of P- and axially chiral phosphorus compounds.

机构信息

College of Chemistry and Chemical Engineering, Yangzhou University, 180 Siwangting Road, 225002, Yangzhou, China.

College of Chemistry and Chemical Engineering, Inner Mongolia University, 235 West University Street, 010021, Hohhot, China.

出版信息

Nat Commun. 2023 Apr 20;14(1):2264. doi: 10.1038/s41467-023-37987-8.

DOI:10.1038/s41467-023-37987-8
PMID:37081007
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10119316/
Abstract

Transition metal-catalyzed C-H bond functionalization is an important method in organic synthesis, but the development of methods that are lower cost and have a less environmental impact is desirable. Here, a Cu-catalyzed asymmetric C(sp)-H arylation is reported. With diaryliodonium salts as arylating reagents, a range of ortho-arylated P-chiral phosphonic diamides were obtained in moderate to excellent yields with high enantioselectivities (up to 92% ee). Meanwhile, enantioselective C-3 arylation of diarylphosphine oxide indoles was also realized under similar conditions to construct axial chirality.

摘要

过渡金属催化的 C-H 键功能化是有机合成中的一种重要方法,但开发成本更低、环境影响更小的方法是可取的。在这里,报道了一种 Cu 催化的不对称 C(sp)-H 芳基化反应。以二芳基碘𬭩盐作为芳基化试剂,在温和至优良的产率下,以高对映选择性(高达 92%ee)获得了一系列邻位芳基化的 P-手性膦酸二酰胺。同时,在类似条件下,也实现了二芳基氧化膦吲哚的对映选择性 C-3 芳基化,构建了轴向手性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/9d1c8c50ce01/41467_2023_37987_Fig8_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/0024057e4ede/41467_2023_37987_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/d2807f0cd8f6/41467_2023_37987_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/7aae0281a151/41467_2023_37987_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/d02086382387/41467_2023_37987_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/b2ee17e4f811/41467_2023_37987_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/614dae22ac1f/41467_2023_37987_Fig6_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/a89e9704466d/41467_2023_37987_Fig7_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/9d1c8c50ce01/41467_2023_37987_Fig8_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/0024057e4ede/41467_2023_37987_Fig1_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/d2807f0cd8f6/41467_2023_37987_Fig2_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/7aae0281a151/41467_2023_37987_Fig3_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/d02086382387/41467_2023_37987_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/b2ee17e4f811/41467_2023_37987_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/614dae22ac1f/41467_2023_37987_Fig6_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/a89e9704466d/41467_2023_37987_Fig7_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b806/10119316/9d1c8c50ce01/41467_2023_37987_Fig8_HTML.jpg

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Cu(I)-Catalyzed Asymmetric Arylation of Pyrroles with Diaryliodonium Salts toward the Synthesis of N-N Atropisomers.
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