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铜催化的芳基硼酸酯的 Suzuki-Miyaura 偶联反应:(PN)CuF 的转金属化作用及中间体的鉴定。

Copper-catalyzed Suzuki-Miyaura coupling of arylboronate esters: transmetalation with (PN)CuF and identification of intermediates.

机构信息

Department of Chemistry & Chemical Biology, University of New Mexico , Albuquerque, New Mexico 87131, United States.

出版信息

Org Lett. 2014 Feb 21;16(4):1264-7. doi: 10.1021/ol500310u. Epub 2014 Feb 5.

DOI:10.1021/ol500310u
PMID:24499358
Abstract

An efficient Cu(I)-catalyzed Suzuki-Miyaura reaction was developed for the coupling of aryl- and heteroarylboronate esters with aryl and heteroaryl iodides at low catalyst loadings (2 mol %). The reaction proceeds under ligand-free conditions for aryl-heteroaryl and heteroaryl-heteroaryl couplings. We also conducted the first detailed mechanistic studies by synthesizing [(PN-2)CuI]2, [(PN-2)CuF]2, and (PN-2)CuPh (PN-2 = o-(di-tert-butylphosphino)-N,N-dimethylaniline) and demonstrated that [(PN-2)CuF]2 is the species that undergoes transmetalation with arylboronate esters.

摘要

发展了一种高效的 Cu(I)催化的 Suzuki-Miyaura 反应,用于在低催化剂负载量(2 mol%)下实现芳基硼酸酯与芳基和杂芳基碘化物的偶联。该反应在无配体条件下进行,适用于芳基-杂芳基和杂芳基-杂芳基偶联。我们还通过合成 [(PN-2)CuI]2、[(PN-2)CuF]2 和 (PN-2)CuPh(PN-2 = o-(二-叔丁基膦基)-N,N-二甲基苯胺)进行了首次详细的机理研究,并证明 [(PN-2)CuF]2 是与芳基硼酸酯进行转金属化的物种。

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