Aryl Halide Radical Clocks as Probes of Stannylene/Aryl Halide C–H Activation Rates

Ajdin Kavara; Michael M. Kheir; Jeff W. Kampf; Mark M. Banaszak Holl

doi:10.1007/s10904-013-9990-y

Aryl Halide Radical Clocks as Probes of Stannylene/Aryl Halide C–H Activation Rates

Ajdin Kavara, Michael M. Kheir, Jeff W. Kampf, Mark M. Banaszak Holl

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

4 Citations (Scopus)

Abstract

Using the radical cyclization induced by the reaction of [InlineMediaObject not available: see fulltext.] (1) with 1-(but-3-en-1-yloxy)-2-iodobenzene, we have determined the rate of allylic and propargylic C–H activation to be 1.1 ± 0.2 × 10⁸ M⁻¹ s⁻¹. The rate of oxidative addition of aryl halide with 1 was estimated to be 10⁷–10⁸ M⁻¹ s⁻¹. The radical cyclization involving 1 and 1-(allyloxy)-2-iodobenzene proceeds quantitatively, indicating that the rate of cyclization (9.6 × 10⁹ s⁻¹) is faster than the rate of hydrocarbon/alkene/alkyne C–H abstraction.

Original language	English
Pages (from-to)	250-257
Number of pages	8
Journal	Journal of Inorganic and Organometallic Polymers and Materials
Volume	24
Issue number	1
DOIs	https://doi.org/10.1007/s10904-013-9990-y
Publication status	Published - 1 Jan 2014
Externally published	Yes

Keywords

C–H activation
Radical clock
Stannylene

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10.1007/s10904-013-9990-y

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abstract = "Using the radical cyclization induced by the reaction of [InlineMediaObject not available: see fulltext.] (1) with 1-(but-3-en-1-yloxy)-2-iodobenzene, we have determined the rate of allylic and propargylic C–H activation to be 1.1 ± 0.2 × 108 M−1 s−1. The rate of oxidative addition of aryl halide with 1 was estimated to be 107–108 M−1 s−1. The radical cyclization involving 1 and 1-(allyloxy)-2-iodobenzene proceeds quantitatively, indicating that the rate of cyclization (9.6 × 109 s−1) is faster than the rate of hydrocarbon/alkene/alkyne C–H abstraction.",

keywords = "C–H activation, Radical clock, Stannylene",

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T1 - Aryl Halide Radical Clocks as Probes of Stannylene/Aryl Halide C–H Activation Rates

AU - Kavara, Ajdin

AU - Kheir, Michael M.

AU - Kampf, Jeff W.

AU - Banaszak Holl, Mark M.

PY - 2014/1/1

Y1 - 2014/1/1

N2 - Using the radical cyclization induced by the reaction of [InlineMediaObject not available: see fulltext.] (1) with 1-(but-3-en-1-yloxy)-2-iodobenzene, we have determined the rate of allylic and propargylic C–H activation to be 1.1 ± 0.2 × 108 M−1 s−1. The rate of oxidative addition of aryl halide with 1 was estimated to be 107–108 M−1 s−1. The radical cyclization involving 1 and 1-(allyloxy)-2-iodobenzene proceeds quantitatively, indicating that the rate of cyclization (9.6 × 109 s−1) is faster than the rate of hydrocarbon/alkene/alkyne C–H abstraction.

AB - Using the radical cyclization induced by the reaction of [InlineMediaObject not available: see fulltext.] (1) with 1-(but-3-en-1-yloxy)-2-iodobenzene, we have determined the rate of allylic and propargylic C–H activation to be 1.1 ± 0.2 × 108 M−1 s−1. The rate of oxidative addition of aryl halide with 1 was estimated to be 107–108 M−1 s−1. The radical cyclization involving 1 and 1-(allyloxy)-2-iodobenzene proceeds quantitatively, indicating that the rate of cyclization (9.6 × 109 s−1) is faster than the rate of hydrocarbon/alkene/alkyne C–H abstraction.

KW - C–H activation

KW - Radical clock

KW - Stannylene

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U2 - 10.1007/s10904-013-9990-y

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VL - 24

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JF - Journal of Inorganic and Organometallic Polymers and Materials

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Aryl Halide Radical Clocks as Probes of Stannylene/Aryl Halide C–H Activation Rates

Abstract

Keywords

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