Method and Mechanistic Insights to 1,2-Aminochlorinate Alkenes using Blue-Light Activated Dichlorocarbamates

Sini Irvankoski; Michael T. Davenport; Daniel H. Ess; Juha H. Siitonen

doi:10.1002/chem.202403215

Method and Mechanistic Insights to 1,2-Aminochlorinate Alkenes using Blue-Light Activated Dichlorocarbamates

Sini Irvankoski, Michael T. Davenport, Daniel H. Ess^*, Juha H. Siitonen^*

^*Corresponding author for this work

Brigham Young University

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

Abstract

Blue light activation of N,N-dichlorocarbamates facilitates a direct 1,2-aminochlorination of unactivated olefins to yield 1,2-chloro-N−Cl compounds under ambient conditions. Mechanistic studies suggest that N,N-dichlorocarbamates undergo a photochemical excitation to yield a neutral nitrogen-centered radical, which rapidly reacts with olefins in an anti-Markovnikov fashion. Using this method, a range of functionally diverse substrates are successfully aminochlorinated to yield the corresponding 1,2-chloro-N−Cl compounds.

Original language	English
Article number	e202403215
Journal	Chemistry - A European Journal
Volume	31
Issue number	22
Early online date	29 Mar 2025
DOIs	https://doi.org/10.1002/chem.202403215
Publication status	Published - 15 Apr 2025
MoE publication type	A1 Journal article-refereed

Keywords

Aminochlorination
DFT
Mechanisms
Photochemistry
TD-DFT

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10.1002/chem.202403215

POPCA: Polyfunctionalization of Olefins through Photoactivation of Chloramines
Siitonen, J. (Principal investigator)
01/09/2023 → 31/08/2027
Project: RCF Academy Research Fellow (new)

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title = "Method and Mechanistic Insights to 1,2-Aminochlorinate Alkenes using Blue-Light Activated Dichlorocarbamates",

abstract = "Blue light activation of N,N-dichlorocarbamates facilitates a direct 1,2-aminochlorination of unactivated olefins to yield 1,2-chloro-N−Cl compounds under ambient conditions. Mechanistic studies suggest that N,N-dichlorocarbamates undergo a photochemical excitation to yield a neutral nitrogen-centered radical, which rapidly reacts with olefins in an anti-Markovnikov fashion. Using this method, a range of functionally diverse substrates are successfully aminochlorinated to yield the corresponding 1,2-chloro-N−Cl compounds.",

keywords = "Aminochlorination, DFT, Mechanisms, Photochemistry, TD-DFT",

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AU - Irvankoski, Sini

AU - Davenport, Michael T.

AU - Ess, Daniel H.

AU - Siitonen, Juha H.

PY - 2025/4/15

Y1 - 2025/4/15

N2 - Blue light activation of N,N-dichlorocarbamates facilitates a direct 1,2-aminochlorination of unactivated olefins to yield 1,2-chloro-N−Cl compounds under ambient conditions. Mechanistic studies suggest that N,N-dichlorocarbamates undergo a photochemical excitation to yield a neutral nitrogen-centered radical, which rapidly reacts with olefins in an anti-Markovnikov fashion. Using this method, a range of functionally diverse substrates are successfully aminochlorinated to yield the corresponding 1,2-chloro-N−Cl compounds.

AB - Blue light activation of N,N-dichlorocarbamates facilitates a direct 1,2-aminochlorination of unactivated olefins to yield 1,2-chloro-N−Cl compounds under ambient conditions. Mechanistic studies suggest that N,N-dichlorocarbamates undergo a photochemical excitation to yield a neutral nitrogen-centered radical, which rapidly reacts with olefins in an anti-Markovnikov fashion. Using this method, a range of functionally diverse substrates are successfully aminochlorinated to yield the corresponding 1,2-chloro-N−Cl compounds.

KW - Aminochlorination

KW - DFT

KW - Mechanisms

KW - Photochemistry

KW - TD-DFT

U2 - 10.1002/chem.202403215

DO - 10.1002/chem.202403215

M3 - Article

AN - SCOPUS:105001149240

SN - 0947-6539

VL - 31

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 22

M1 - e202403215

ER -

Method and Mechanistic Insights to 1,2-Aminochlorinate Alkenes using Blue-Light Activated Dichlorocarbamates

Abstract

Keywords

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Projects

POPCA: Polyfunctionalization of Olefins through Photoactivation of Chloramines

Cite this