配体加速的 C(sp2)-H 键与芳基硼试剂的交叉偶联反应。
Ligand-accelerated cross-coupling of C(sp2)-H bonds with arylboron reagents.
机构信息
Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
出版信息
J Am Chem Soc. 2011 Nov 16;133(45):18183-93. doi: 10.1021/ja203978r. Epub 2011 Oct 21.
Abstract
A ligand-accelerated Pd(II)-catalyzed C(sp(2))-H/arylboron cross-coupling reaction of phenylacetic acid substrates is reported. Using Ac-Ile-OH as the ligand and Ag(2)CO(3) as the oxidant, a fast, high-yielding, operationally simple, and functional group-tolerant protocol has been developed for the cross-coupling of phenylacetic acid substrates with aryltrifluoroborates. This ligand scaffold has also been shown to improve catalysis using 1 atm O(2) as the sole reoxidant, which sheds light on the path forward in developing optimized ligands for aerobic C-H/arylboron cross-coupling.
摘要
报道了一种配体加速的 Pd(II)催化的 C(sp(2))-H/芳基硼酸交叉偶联反应，涉及苯乙酸底物。使用 Ac-Ile-OH 作为配体和 Ag(2)CO(3)作为氧化剂，开发了一种快速、高产、操作简单且官能团容忍的苯乙酸底物与芳基三氟硼酸盐交叉偶联的方法。该配体支架还被证明可以改善使用 1 atm O(2)作为唯一氧化剂的催化作用，为开发有氧 C-H/芳基硼酸交叉偶联的优化配体指明了方向。
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本文引用的文献
1
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Inorg Chem. 2011 Sep 5;50(17):8132-43. doi: 10.1021/ic200564d. Epub 2011 Aug 1.
2
Reaction of O2 with [(-)-sparteine]Pd(H)Cl: evidence for an intramolecular [H-L]+ "reductive elimination" pathway.O2 与 [(-)-sparteine]Pd(H)Cl 的反应：支持分子内 [H-L]+“还原消除”途径的证据。
J Am Chem Soc. 2011 Aug 31;133(34):13268-71. doi: 10.1021/ja204989p. Epub 2011 Aug 4.
3
Silanol: a traceless directing group for Pd-catalyzed o-alkenylation of phenols.硅醇：一种用于 Pd 催化的酚的邻烯丙基化的无痕迹导向基团。
J Am Chem Soc. 2011 Aug 17;133(32):12406-9. doi: 10.1021/ja204924j. Epub 2011 Jul 21.
4
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J Am Chem Soc. 2011 Jul 20;133(28):10716-9. doi: 10.1021/ja202975w. Epub 2011 Jun 23.
5
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Org Lett. 2011 Jul 15;13(14):3640-3. doi: 10.1021/ol201292v. Epub 2011 Jun 21.
6
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Science. 2011 Jul 8;333(6039):209-13. doi: 10.1126/science.1204183. Epub 2011 Jun 9.
7
Synthesis of dibenzofurans via palladium-catalyzed phenol-directed C-H activation/C-O cyclization.通过钯催化的酚导向的 C-H 活化/C-O 环化合成二苯并呋喃。
J Am Chem Soc. 2011 Jun 22;133(24):9250-3. doi: 10.1021/ja203335u. Epub 2011 May 31.
8
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Isr J Chem. 2010 Dec;50(5-6):605-616. doi: 10.1002/ijch.201000038.
9
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J Am Chem Soc. 2011 May 11;133(18):7222-8. doi: 10.1021/ja201708f. Epub 2011 Apr 13.
10
Benzoquinone-promoted reaction of O2 with a Pd(II)-hydride.苯醌促进的 O2 与 Pd(II)-氢化物反应。
J Am Chem Soc. 2011 Apr 20;133(15):5732-5. doi: 10.1021/ja200957n. Epub 2011 Mar 25.
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