Manganese(I)-Catalyzed C−H Activation: The Key Role of a 7-Membered Manganacycle in H-Transfer and Reductive Elimination

Nasiru P. Yahaya; Kate M. Appleby; Magdalene Teh; Conrad Wagner; Erik Troschke; Joshua T W Bray; Simon B. Duckett; L. Anders Hammarback; Jonathan S. Ward; Jessica Milani; Natalie E. Pridmore; Adrian C. Whitwood; Jason M. Lynam; Ian J S Fairlamb

doi:10.1002/anie.201606236

Manganese(I)-Catalyzed C−H Activation: The Key Role of a 7-Membered Manganacycle in H-Transfer and Reductive Elimination

Nasiru P. Yahaya, Kate M. Appleby, Magdalene Teh, Conrad Wagner, Erik Troschke, Joshua T W Bray, Simon B. Duckett, L. Anders Hammarback, Jonathan S. Ward, Jessica Milani, Natalie E. Pridmore, Adrian C. Whitwood, Jason M. Lynam^*, Ian J S Fairlamb

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Manganese-catalyzed C−H bond activation chemistry is emerging as a powerful and complementary method for molecular functionalization. A highly reactive seven-membered Mn^Iintermediate is detected and characterized that is effective for H-transfer or reductive elimination to deliver alkenylated or pyridinium products, respectively. The two pathways are determined at Mn^Iby judicious choice of an electron-deficient 2-pyrone substrate containing a 2-pyridyl directing group, which undergoes regioselective C−H bond activation, serving as a valuable system for probing the mechanistic features of Mn C−H bond activation chemistry.

Original language	English
Pages (from-to)	12455-12459
Number of pages	5
Journal	Angewandte Chemie International Edition
Volume	55
Issue number	40
Early online date	7 Sept 2016
DOIs	https://doi.org/10.1002/anie.201606236
Publication status	Published - 26 Sept 2016

Bibliographical note

Keywords

catalysis
C−H activation
functionalization
manganese
sustainability

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acie_fairlamb_lynam_pureAccepted author manuscript, 7.46 MBLicence: CC BY
Yahaya_et_al-2016-Angewandte_Chemie_International_Edition
© 2016, The Authors.
Final published version, 1.93 MBLicence: CC BY

Cite this

Yahaya, N. P., Appleby, K. M., Teh, M., Wagner, C., Troschke, E., Bray, J. T. W., Duckett, S. B., Hammarback, L. A., Ward, J. S., Milani, J., Pridmore, N. E., Whitwood, A. C., Lynam, J. M., & Fairlamb, I. J. S. (2016). Manganese(I)-Catalyzed C−H Activation: The Key Role of a 7-Membered Manganacycle in H-Transfer and Reductive Elimination. Angewandte Chemie International Edition, 55(40), 12455-12459. https://doi.org/10.1002/anie.201606236

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abstract = "Manganese-catalyzed C−H bond activation chemistry is emerging as a powerful and complementary method for molecular functionalization. A highly reactive seven-membered MnIintermediate is detected and characterized that is effective for H-transfer or reductive elimination to deliver alkenylated or pyridinium products, respectively. The two pathways are determined at MnIby judicious choice of an electron-deficient 2-pyrone substrate containing a 2-pyridyl directing group, which undergoes regioselective C−H bond activation, serving as a valuable system for probing the mechanistic features of Mn C−H bond activation chemistry.",

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author = "Yahaya, {Nasiru P.} and Appleby, {Kate M.} and Magdalene Teh and Conrad Wagner and Erik Troschke and Bray, {Joshua T W} and Duckett, {Simon B.} and Hammarback, {L. Anders} and Ward, {Jonathan S.} and Jessica Milani and Pridmore, {Natalie E.} and Whitwood, {Adrian C.} and Lynam, {Jason M.} and Fairlamb, {Ian J S}",

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doi = "10.1002/anie.201606236",

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Yahaya, NP, Appleby, KM, Teh, M, Wagner, C, Troschke, E, Bray, JTW , Duckett, SB, Hammarback, LA, Ward, JS, Milani, J, Pridmore, NE, Whitwood, AC, Lynam, JM & Fairlamb, IJS 2016, 'Manganese(I)-Catalyzed C−H Activation: The Key Role of a 7-Membered Manganacycle in H-Transfer and Reductive Elimination', Angewandte Chemie International Edition, vol. 55, no. 40, pp. 12455-12459. https://doi.org/10.1002/anie.201606236

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T1 - Manganese(I)-Catalyzed C−H Activation

T2 - The Key Role of a 7-Membered Manganacycle in H-Transfer and Reductive Elimination

AU - Yahaya, Nasiru P.

AU - Appleby, Kate M.

AU - Teh, Magdalene

AU - Wagner, Conrad

AU - Troschke, Erik

AU - Bray, Joshua T W

AU - Duckett, Simon B.

AU - Hammarback, L. Anders

AU - Ward, Jonathan S.

AU - Milani, Jessica

AU - Pridmore, Natalie E.

AU - Whitwood, Adrian C.

AU - Lynam, Jason M.

AU - Fairlamb, Ian J S

PY - 2016/9/26

Y1 - 2016/9/26

N2 - Manganese-catalyzed C−H bond activation chemistry is emerging as a powerful and complementary method for molecular functionalization. A highly reactive seven-membered MnIintermediate is detected and characterized that is effective for H-transfer or reductive elimination to deliver alkenylated or pyridinium products, respectively. The two pathways are determined at MnIby judicious choice of an electron-deficient 2-pyrone substrate containing a 2-pyridyl directing group, which undergoes regioselective C−H bond activation, serving as a valuable system for probing the mechanistic features of Mn C−H bond activation chemistry.

AB - Manganese-catalyzed C−H bond activation chemistry is emerging as a powerful and complementary method for molecular functionalization. A highly reactive seven-membered MnIintermediate is detected and characterized that is effective for H-transfer or reductive elimination to deliver alkenylated or pyridinium products, respectively. The two pathways are determined at MnIby judicious choice of an electron-deficient 2-pyrone substrate containing a 2-pyridyl directing group, which undergoes regioselective C−H bond activation, serving as a valuable system for probing the mechanistic features of Mn C−H bond activation chemistry.

KW - catalysis

KW - C−H activation

KW - functionalization

KW - manganese

KW - sustainability

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U2 - 10.1002/anie.201606236

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Manganese(I)-Catalyzed C−H Activation: The Key Role of a 7-Membered Manganacycle in H-Transfer and Reductive Elimination

Abstract

Bibliographical note

Keywords

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Simon B. Duckett

Ian James Stewart Fairlamb

Jason Martin Lynam

Syngenta Full Industrial CASE AWARD

New Ruthenium Catalysts for C-C bond Formation: A Combined Experimantal and Theoretical Approach

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Manganese(I)-Catalyzed C−H Activation: The Key Role of a 7-Membered Manganacycle in H-Transfer and Reductive Elimination

Abstract

Bibliographical note

Keywords

Access to Document

Other files and links

Profiles

Simon B. Duckett

Ian James Stewart Fairlamb

Jason Martin Lynam

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Syngenta Full Industrial CASE AWARD

New Ruthenium Catalysts for C-C bond Formation: A Combined Experimantal and Theoretical Approach

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