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

35 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",

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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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