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タイトル: Palladium-catalyzed regioselective and stereo-invertive ring-opening borylation of 2-arylaziridines with bis(pinacolato)diboron: Experimental and computational studies
著者: Takeda, Youhei
Kuroda, Akinobu
Sameera, W. M C
Morokuma, Keiji
Minakata, Satoshi
著者名の別形: 諸熊, 奎治
発行日: 9-Jun-2016
出版者: Royal Society of Chemistry
誌名: Chemical Science
巻: 7
開始ページ: 6141
終了ページ: 6152
抄録: A palladium catalyzed regioselective borylative ring opening reaction of 2-arylaziridines to give β-amino-β-arylethylborates was developed. The reaction reported herein represents the first example of ring-opening borylation of non-vinylic aziridines and direct borylative C(sp3)-N bond cleavage of neutral organic substrates. NMR studies and density functional theory (DFT) calculations suggested that the active intermediate for the reaction is a PdL2 complex [L = P(t-Bu)2Me]. The multi-component artificial force-induced reaction method (MC-AFIR) located the transition states for the regioselectivity-determining aziridine ring opening that proceeds in an SN2 fashion, and explained the selectivity of the reaction. The full catalytic cycle consists of a selectivity-determining aziridine ring opening (oxidative addition), a proton transfer, phosphine ligand dissociation from the catalyst, boron-boron bond cleavage, and reductive elimination. Water is important to the drive the transmetalation step. The calculated overall mechanism and selectivity are consistent with the experimental results.
著作権等: © 2016 The Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
URI: http://hdl.handle.net/2433/216975
DOI(出版社版): 10.1039/c6sc01120a
出現コレクション:学術雑誌掲載論文等

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