Anti-Markovnikov Hydroamination of Unactivated Alkenes with Primary Alkyl Amines

David C. Miller; Jacob M. Ganley; Andrew J. Musacchio; Trevor C. Sherwood; William R. Ewing; Robert R. Knowles

doi:10.1021/jacs.9b08746

Anti-Markovnikov Hydroamination of Unactivated Alkenes with Primary Alkyl Amines

David C. Miller, Jacob M. Ganley, Andrew J. Musacchio, Trevor C. Sherwood, William R. Ewing, Robert R. Knowles

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

72 Scopus citations

Abstract

We report here a photocatalytic method for the intermolecular anti-Markovnikov hydroamination of unactivated olefins with primary alkyl amines to selectively furnish secondary amine products. These reactions proceed through aminium radical cation (ARC) intermediates and occur at room temperature under visible light irradiation in the presence of an iridium photocatalyst and an aryl thiol hydrogen atom donor. Despite the presence of excess olefin, high selectivities are observed for secondary over tertiary amine products, even though the secondary amines are established substrates for ARC-based olefin amination under similar conditions.

Original language	English (US)
Pages (from-to)	16590-16594
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	141
Issue number	42
DOIs	https://doi.org/10.1021/jacs.9b08746
State	Published - Oct 23 2019

All Science Journal Classification (ASJC) codes

Chemistry(all)
Biochemistry
Catalysis
Colloid and Surface Chemistry

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10.1021/jacs.9b08746

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title = "Anti-Markovnikov Hydroamination of Unactivated Alkenes with Primary Alkyl Amines",

abstract = "We report here a photocatalytic method for the intermolecular anti-Markovnikov hydroamination of unactivated olefins with primary alkyl amines to selectively furnish secondary amine products. These reactions proceed through aminium radical cation (ARC) intermediates and occur at room temperature under visible light irradiation in the presence of an iridium photocatalyst and an aryl thiol hydrogen atom donor. Despite the presence of excess olefin, high selectivities are observed for secondary over tertiary amine products, even though the secondary amines are established substrates for ARC-based olefin amination under similar conditions.",

author = "Miller, {David C.} and Ganley, {Jacob M.} and Musacchio, {Andrew J.} and Sherwood, {Trevor C.} and Ewing, {William R.} and Knowles, {Robert R.}",

note = "Funding Information: Financial support was provided by the NIH (R01 GM120530) and Bristol-Myers Squibb. The authors acknowledge Qilei Zhu for helpful conversations. Daniel Nocera, Rui Sun, and Yangzhong Qin are acknowledged for helpful discussions and spectroscopic experiments. Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

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doi = "10.1021/jacs.9b08746",

language = "English (US)",

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T1 - Anti-Markovnikov Hydroamination of Unactivated Alkenes with Primary Alkyl Amines

AU - Miller, David C.

AU - Ganley, Jacob M.

AU - Musacchio, Andrew J.

AU - Sherwood, Trevor C.

AU - Ewing, William R.

AU - Knowles, Robert R.

N1 - Funding Information: Financial support was provided by the NIH (R01 GM120530) and Bristol-Myers Squibb. The authors acknowledge Qilei Zhu for helpful conversations. Daniel Nocera, Rui Sun, and Yangzhong Qin are acknowledged for helpful discussions and spectroscopic experiments. Publisher Copyright: Copyright © 2019 American Chemical Society.

PY - 2019/10/23

Y1 - 2019/10/23

N2 - We report here a photocatalytic method for the intermolecular anti-Markovnikov hydroamination of unactivated olefins with primary alkyl amines to selectively furnish secondary amine products. These reactions proceed through aminium radical cation (ARC) intermediates and occur at room temperature under visible light irradiation in the presence of an iridium photocatalyst and an aryl thiol hydrogen atom donor. Despite the presence of excess olefin, high selectivities are observed for secondary over tertiary amine products, even though the secondary amines are established substrates for ARC-based olefin amination under similar conditions.

AB - We report here a photocatalytic method for the intermolecular anti-Markovnikov hydroamination of unactivated olefins with primary alkyl amines to selectively furnish secondary amine products. These reactions proceed through aminium radical cation (ARC) intermediates and occur at room temperature under visible light irradiation in the presence of an iridium photocatalyst and an aryl thiol hydrogen atom donor. Despite the presence of excess olefin, high selectivities are observed for secondary over tertiary amine products, even though the secondary amines are established substrates for ARC-based olefin amination under similar conditions.

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IS - 42

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Anti-Markovnikov Hydroamination of Unactivated Alkenes with Primary Alkyl Amines

Abstract

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