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Remote C–H Activation via Through-Space Palladium and Rhodium Migrations

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C-H Activation

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 292))

Abstract

The catalytic activation of a C–H bond is a fundamentally important organic transformation. There are now numerous reports of palladium-mediated C–H activation by the through-space interaction of a palladium center with a neighboring C–H bond. This type of C–H activation can lead to a net “palladium migration” from the carbon atom where the palladium is first introduced to a remote carbon atom where C–H activation occurs. This process provides a novel method to introduce a palladium moiety into a position where direct palladium introduction may not be straightforward. This process is accompanied by concurrent migration of a hydrogen atom in the direction opposite to that of the palladium migration. Analogous rhodium migrations have also been reported. In this account, different types of palladium and rhodium migrations are reviewed and the reaction mechanism is discussed.

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Abbreviations

Ac:

Acetyl

acac:

Acetylacetonate

BINAP:

2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl

Boc:

tert-Butoxycarbonyl

Bz:

Benzoyl

cod:

1,5-Cyclooctadiene

dba:

Di(benzylidene)acetone

DMAc:

N,N-Dimethylacetamide

DMF:

N,N-Dimethylformamide

dppb:

1,4-Bis(diphenylphosphino)butane

dppm:

Bis(diphenylphosphino)methane

dppp:

1,3-Bis(diphenylphosphino)propane

Ms:

Methanesulfonyl

Piv:

Pivaloyl

TBAB:

Tetrabutylammonium bromide

TBAC:

Tetrabutylammonium chloride

TES:

Triethylsilyl

Tol:

Tolyl

Tol-BINAP:

2,2′-Bis[di(o-tolyl)phosphino]-1,1′-binaphthyl

S-phos:

2,6-Dimethoxy-2′-(diphenylphosphino)biphenyl

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Author information

Authors and Affiliations

  1. Department of Chemistry, Iowa State University, Ames, IA 50010, USA

    Feng Shi & Richard C. Larock

Authors
  1. Feng Shi
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  2. Richard C. Larock
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Correspondence to Richard C. Larock .

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Editors and Affiliations

  1. Scripps Research Institute, N.Torrey Pines Rd. 10550, La Jolla, 92037, USA

    Jin-Quan Yu

  2. College of Chemistry, Peking University, Chengfu Road 202, Beijing, 100871, China, People's Republic

    Zhangjie Shi

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© 2009 Springer-Verlag Berlin Heidelberg

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Shi, F., Larock, R.C. (2009). Remote C–H Activation via Through-Space Palladium and Rhodium Migrations. In: Yu, JQ., Shi, Z. (eds) C-H Activation. Topics in Current Chemistry, vol 292. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2008_46

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