Reactions of Boron-Derived Radicals with Nucleophiles
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- 作者：Lauren E. Longobardi ; Pavel Zatsepin ; Roman Korol ; Lei Liu ; Stefan Grimme ; Douglas W. Stephan
- 刊名：Journal of the American Chemical Society
- 出版年：2017
- 出版时间：January 11, 2017
- 年：2017
- 卷：139
- 期：1
- 页码：426-435
- 全文大小：634K
- ISSN：1520-5126
文摘
Reactions of phenanthrenedione- and pyrenedione-derived borocyclic radicals, CnH8O2B(C6F5)2• (n = 14 (1), 16 (3)), with a variety of nucleophiles have been studied. Reaction of 1 with P(t-Bu)3 affords the zwitterion 3-(t-Bu)3PC14H7O2B(C6F5)2 (5) in addition to the salt [HP(t-Bu)3][C14H8O2B(C6F5)2] (6). In contrast, the reaction of 1 with PPh3 proceeds to give two regioisomeric zwitterions, 1-(Ph3P)C14H7O2B(C6F5)2 (7a) and 3-(Ph3P)C14H7O2B(C6F5)2 (7b), as well as the related boronic ester C14H8O2B(C6F5) (2). In a similar fashion, 3 reacted with PPh3 to give 3-(Ph3P)C16H7O2B(C6F5)2 (8a), 1-(Ph3P)C16H7O2B(C6F5)2 (8b), and boronic ester C16H8O2B(C6F5) (4). Reactions of secondary phosphines Ph2PH and tBu2PH with 3 yield 3-(R2PH)C16H7O2B(C6F5)2 (R = Ph (9), t-Bu (10)). The reaction of 1 with N-heterocyclic carbene IMes afforded 3-(IMes)C14H7O2B(C6F5)2 (11) and [IMesH][C14H8O2B(C6F5)2] (12), while the reactions with quinuclidine and DMAP afforded the species 3-(C7H13N)C14H7O2B(C6F5)2 (13) and [H(NC7H13)2][C14H8O2B(C6F5)2] (14), and the salt [9,10-(DMAP)2C14H8O2B(C6F5)2][C14H8O2B(C6F5)2] (15), respectively. These products have been fully characterized, and the mechanism for the formation of these products is considered in the light of DFT calculations.