X-ray Absorption and EPR Evidence for a Single Electron Redox Process in Copper Catalysis

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2017 Jul 19

PMID 28717490

Citations 2

Authors

Qingquan Lu

Jian Zhang

Pan Peng

Guanghui Zhang

Zhiliang Huang

Hong Yi

Jeffrey T Miller

Aiwen Lei

Affiliations

Soon will be listed here.

Abstract

An unprecedented single electron redox process in copper catalysis is confirmed using X-ray absorption and EPR spectroscopies. The oxidation state of the copper species in the interaction between Cu(ii) and a sulfinic acid at room temperature, and the accurate characterization of the formed Cu(i) are clearly shown using X-ray absorption and EPR evidence. Further investigation of anion effects on Cu(ii) discloses that bromine ions can dramatically increase the rate of the redox process. Moreover, it is proven that the sulfinic acids are converted into sulfonyl radicals, which can be trapped by 2-arylacrylic acids and various valuable β-keto sulfones are synthesized with good to excellent yields under mild conditions.

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References

Evano G, Blanchard N, Toumi M . Copper-mediated coupling reactions and their applications in natural products and designed biomolecules synthesis. Chem Rev. 2008; 108(8):3054-131. DOI: 10.1021/cr8002505. View

Kosman D . Multicopper oxidases: a workshop on copper coordination chemistry, electron transfer, and metallophysiology. J Biol Inorg Chem. 2009; 15(1):15-28. DOI: 10.1007/s00775-009-0590-9. View

Enthaler S, Junge K, Beller M . Sustainable metal catalysis with iron: from rust to a rising star?. Angew Chem Int Ed Engl. 2008; 47(18):3317-21. DOI: 10.1002/anie.200800012. View

Ma D, Cai Q . Copper/amino acid catalyzed cross-couplings of aryl and vinyl halides with nucleophiles. Acc Chem Res. 2008; 41(11):1450-60. DOI: 10.1021/ar8000298. View

Solomon E, Chen P, Metz M, Lee S, Palmer A . Oxygen Binding, Activation, and Reduction to Water by Copper Proteins. Angew Chem Int Ed Engl. 2002; 40(24):4570-4590. DOI: 10.1002/1521-3773(20011217)40:24<4570::aid-anie4570>3.0.co;2-4. View

Yamada K, Tomioka K . Copper-catalyzed asymmetric alkylation of imines with dialkylzinc and related reactions. Chem Rev. 2008; 108(8):2874-86. DOI: 10.1021/cr078370u. View

Zhang G, Yi H, Zhang G, Deng Y, Bai R, Zhang H . Direct observation of reduction of Cu(II) to Cu(I) by terminal alkynes. J Am Chem Soc. 2014; 136(3):924-6. DOI: 10.1021/ja410756b. View

King A, Ryland B, Brunold T, Stahl S . Kinetic and Spectroscopic Studies of Aerobic Copper(II)-Catalyzed Methoxylation of Arylboronic Esters and Insights into Aryl Transmetalation to Copper(II). Organometallics. 2012; 31(22):7948-7957. PMC: 3509420. DOI: 10.1021/om300586p. View

Jutand A . Contribution of electrochemistry to organometallic catalysis. Chem Rev. 2008; 108(7):2300-47. DOI: 10.1021/cr068072h. View

10.

Chufan E, Puiu S, Karlin K . Heme-copper/dioxygen adduct formation, properties, and reactivity. Acc Chem Res. 2007; 40(7):563-72. DOI: 10.1021/ar700031t. View

11.

Stanley L, Sibi M . Enantioselective copper-catalyzed 1,3-dipolar cycloadditions. Chem Rev. 2008; 108(8):2887-902. DOI: 10.1021/cr078371m. View

12.

Sambiagio C, Marsden S, Blacker A, McGowan P . Copper catalysed Ullmann type chemistry: from mechanistic aspects to modern development. Chem Soc Rev. 2014; 43(10):3525-50. DOI: 10.1039/c3cs60289c. View

13.

Bolm C, Legros J, Le Paih J, Zani L . Iron-catalyzed reactions in organic synthesis. Chem Rev. 2004; 104(12):6217-54. DOI: 10.1021/cr040664h. View

14.

Rolff M, Schottenheim J, Decker H, Tuczek F . Copper-O2 reactivity of tyrosinase models towards external monophenolic substrates: molecular mechanism and comparison with the enzyme. Chem Soc Rev. 2011; 40(7):4077-98. DOI: 10.1039/c0cs00202j. View

15.

Pintauer T, Matyjaszewski K . Atom transfer radical addition and polymerization reactions catalyzed by ppm amounts of copper complexes. Chem Soc Rev. 2008; 37(6):1087-97. DOI: 10.1039/b714578k. View

16.

Franc G, Jutand A . On the origin of copper(I) catalysts from copper(II) precursors in C-N and C-O cross-couplings. Dalton Trans. 2010; 39(34):7873-5. DOI: 10.1039/c0dt00632g. View

17.

Kapdi A, Whitwood A, Williamson D, Lynam J, Burns M, Williams T . The elusive structure of Pd2(dba)3. Examination by isotopic labeling, NMR spectroscopy, and X-ray diffraction analysis: synthesis and characterization of Pd2(dba-Z)3 complexes. J Am Chem Soc. 2013; 135(22):8388-99. DOI: 10.1021/ja403259c. View

18.

Ellis P, Fairlamb I, Hackett S, Wilson K, Lee A . Evidence for the surface-catalyzed Suzuki-Miyaura reaction over palladium nanoparticles: an operando XAS study. Angew Chem Int Ed Engl. 2010; 49(10):1820-4. DOI: 10.1002/anie.200906675. View

19.

Alexakis A, Backvall J, Krause N, Pamies O, Dieguez M . Enantioselective copper-catalyzed conjugate addition and allylic substitution reactions. Chem Rev. 2008; 108(8):2796-823. DOI: 10.1021/cr0683515. View

20.

Wendlandt A, Suess A, Stahl S . Copper-catalyzed aerobic oxidative C-H functionalizations: trends and mechanistic insights. Angew Chem Int Ed Engl. 2011; 50(47):11062-87. DOI: 10.1002/anie.201103945. View