Palladium-Catalyzed Divergent Cyclopropanation by Regioselective Solvent-Driven C(sp3)−H Bond Activation

Da Sol Chung; Jae Sung Lee; Ho Ryu; Jiyong Park; Hyunjoong Kim; Joo Hyun Lee; U. Bin Kim; Won Koo Lee; Mu Hyun Baik; Sang gi Lee

doi:10.1002/anie.201809133

Palladium-Catalyzed Divergent Cyclopropanation by Regioselective Solvent-Driven C(sp³)−H Bond Activation

Da Sol Chung, Jae Sung Lee, Ho Ryu, Jiyong Park, Hyunjoong Kim, Joo Hyun Lee, U. Bin Kim, Won Koo Lee, Mu Hyun Baik, Sang gi Lee

Department of Chemistry & Nanoscience

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

32 Scopus citations

Abstract

Reported is a tandem palladium-catalyzed Heck/regioselective C(sp³)−H activation reaction for the divergent synthesis of spiro- and fused-cyclopropanated indolines from N-methallylated 2-bromoarylamides. The regioselectivity of the C−H bond activation in the σ-alkylPd^II intermediate is controlled by the solvent used. DFT calculations suggest that the polarity of solvent molecules could influence the transition-state energy, leading to a bifurcation of the C−H bond activation in the σ-alkylPd^II intermediate.

Original language	English
Pages (from-to)	15460-15464
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	47
DOIs	https://doi.org/10.1002/anie.201809133
State	Published - 19 Nov 2018

Bibliographical note

Funding Information:
This work was made possible by the support of the National Research Foundation (NRF-2016R1A2B2013727). D.S.C. acknowledges the Solvay Fellowship. We thank Dr. Y. Kim for X-ray analysis. We also thank Prof. S. Chang at KAIST for use of the time-resolved infrared spectrometer. M.-H.B. acknowledges the financial support from the Institute for Basic Science (IBS-R10-D1).

Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

C−H activation
heterocylces
palladium
reaction mechanisms
solvent effects

Access to Document

10.1002/anie.201809133

Cite this

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title = "Palladium-Catalyzed Divergent Cyclopropanation by Regioselective Solvent-Driven C(sp3)−H Bond Activation",

abstract = "Reported is a tandem palladium-catalyzed Heck/regioselective C(sp3)−H activation reaction for the divergent synthesis of spiro- and fused-cyclopropanated indolines from N-methallylated 2-bromoarylamides. The regioselectivity of the C−H bond activation in the σ-alkylPdII intermediate is controlled by the solvent used. DFT calculations suggest that the polarity of solvent molecules could influence the transition-state energy, leading to a bifurcation of the C−H bond activation in the σ-alkylPdII intermediate.",

keywords = "C−H activation, heterocylces, palladium, reaction mechanisms, solvent effects",

author = "Chung, \{Da Sol\} and Lee, \{Jae Sung\} and Ho Ryu and Jiyong Park and Hyunjoong Kim and Lee, \{Joo Hyun\} and Kim, \{U. Bin\} and Lee, \{Won Koo\} and Baik, \{Mu Hyun\} and Lee, \{Sang gi\}",

note = "Funding Information: This work was made possible by the support of the National Research Foundation (NRF-2016R1A2B2013727). D.S.C. acknowledges the Solvay Fellowship. We thank Dr. Y. Kim for X-ray analysis. We also thank Prof. S. Chang at KAIST for use of the time-resolved infrared spectrometer. M.-H.B. acknowledges the financial support from the Institute for Basic Science (IBS-R10-D1). Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2018",

month = nov,

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doi = "10.1002/anie.201809133",

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AU - Chung, Da Sol

AU - Lee, Jae Sung

AU - Ryu, Ho

AU - Park, Jiyong

AU - Kim, Hyunjoong

AU - Lee, Joo Hyun

AU - Kim, U. Bin

AU - Lee, Won Koo

AU - Baik, Mu Hyun

AU - Lee, Sang gi

N1 - Funding Information: This work was made possible by the support of the National Research Foundation (NRF-2016R1A2B2013727). D.S.C. acknowledges the Solvay Fellowship. We thank Dr. Y. Kim for X-ray analysis. We also thank Prof. S. Chang at KAIST for use of the time-resolved infrared spectrometer. M.-H.B. acknowledges the financial support from the Institute for Basic Science (IBS-R10-D1). Publisher Copyright: © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2018/11/19

Y1 - 2018/11/19

N2 - Reported is a tandem palladium-catalyzed Heck/regioselective C(sp3)−H activation reaction for the divergent synthesis of spiro- and fused-cyclopropanated indolines from N-methallylated 2-bromoarylamides. The regioselectivity of the C−H bond activation in the σ-alkylPdII intermediate is controlled by the solvent used. DFT calculations suggest that the polarity of solvent molecules could influence the transition-state energy, leading to a bifurcation of the C−H bond activation in the σ-alkylPdII intermediate.

AB - Reported is a tandem palladium-catalyzed Heck/regioselective C(sp3)−H activation reaction for the divergent synthesis of spiro- and fused-cyclopropanated indolines from N-methallylated 2-bromoarylamides. The regioselectivity of the C−H bond activation in the σ-alkylPdII intermediate is controlled by the solvent used. DFT calculations suggest that the polarity of solvent molecules could influence the transition-state energy, leading to a bifurcation of the C−H bond activation in the σ-alkylPdII intermediate.

KW - C−H activation

KW - heterocylces

KW - palladium

KW - reaction mechanisms

KW - solvent effects

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