home > Pablication
2024
2023
2022
2021
2020
2019
2018
2017
2016 2015 2014 2013 2012 2011 2010 2009
2008 1998–2007
Kensuke Kiyokawa,* Kazuki Kawanaka, and Satoshi Minakata*
Angew. Chem. Int. Ed. Early View. DOI:10.1002/anie.202319048
*Open-Access Article"!
*Selected as a HOT Paper"!
Abstract: In this report, we describe the use of amino-λ3-iodanes in the electrophilic amination of arylboronic acids and boronates. Iodine(III) reagents with transferable amino groups, including one with an NH2 group, were synthesized and used in the amination, allowing the synthesis of a wide range of primary and secondary (hetero)arylamines. Mechanistic studies by DFT calculations indicate that the reaction proceeds through an electrophilic amination process from a tetravalent borate complex with a B−N dative bond.
Daichi Okumatsu, Kensuke Kiyokawa,* Linh Tran Bao Nguyen, Manabu Abe* and Satoshi Minakata*
Chem. Sci. 2024, 15, 1069-1076. DOI:10.1039/D3SC06090Jz
Abstract: The alkylamination of alkenes using pristine carboxylic acids was achieved by the photoexcitation of (diarylmethylene)amino benziodoxolones (DABXs), which serve as both an oxidant and an aminating reagent (an iminyl radical precursor). The developed method is a simple photochemical reaction without the need for external photosensitizers and shows a broad substrate scope for aliphatic carboxylic acids leading to the formation of primary, secondary, and tertiary alkyl radicals, thus enabling the facile synthesis of various structurally complex amines. Mechanistic investigations including transient absorption spectroscopy measurements using a laser flash photolysis (LFP) method disclosed the unique photochemical reactivity of DABXs, which undergoes homolysis of their I–N bonds to give an iminyl radical and ortho-iodobenzoyloxy radical, the latter of which participates in the single-electron oxidation of carboxylates.
2016 2015 2014 2013 2012 2011 2010 2009
2008 1998–2007
“Amino-λ3-iodane-Enabled Electrophilic Amination of Arylboronic Acid Derivatives"
Kensuke Kiyokawa,* Kazuki Kawanaka, and Satoshi Minakata*
Angew. Chem. Int. Ed. Early View. DOI:10.1002/anie.202319048
*Open-Access Article"!
*Selected as a HOT Paper"!
Abstract: In this report, we describe the use of amino-λ3-iodanes in the electrophilic amination of arylboronic acids and boronates. Iodine(III) reagents with transferable amino groups, including one with an NH2 group, were synthesized and used in the amination, allowing the synthesis of a wide range of primary and secondary (hetero)arylamines. Mechanistic studies by DFT calculations indicate that the reaction proceeds through an electrophilic amination process from a tetravalent borate complex with a B−N dative bond.
“Photoexcitation of (Diarylmethylene)amino Benziodoxolones for Alkylamination of Styrene Derivatives with Carboxylic Acids"
Daichi Okumatsu, Kensuke Kiyokawa,* Linh Tran Bao Nguyen, Manabu Abe* and Satoshi Minakata*
Chem. Sci. 2024, 15, 1069-1076. DOI:10.1039/D3SC06090Jz
Abstract: The alkylamination of alkenes using pristine carboxylic acids was achieved by the photoexcitation of (diarylmethylene)amino benziodoxolones (DABXs), which serve as both an oxidant and an aminating reagent (an iminyl radical precursor). The developed method is a simple photochemical reaction without the need for external photosensitizers and shows a broad substrate scope for aliphatic carboxylic acids leading to the formation of primary, secondary, and tertiary alkyl radicals, thus enabling the facile synthesis of various structurally complex amines. Mechanistic investigations including transient absorption spectroscopy measurements using a laser flash photolysis (LFP) method disclosed the unique photochemical reactivity of DABXs, which undergoes homolysis of their I–N bonds to give an iminyl radical and ortho-iodobenzoyloxy radical, the latter of which participates in the single-electron oxidation of carboxylates.