- Iodonium Cyclophanes for SECURE Arene Functionalization
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This disclosure relates to compounds, reagents, and methods useful in the synthesis of aryl fluorides, for example, in the preparation of 18F labeled radiotracers. For example, this disclosure provides universal “locked” aryl substituents that result in StereoElectronic Control of Unidirectional Reductive Elimination (SECURE) from diaryliodonium salts. The reagents and methods provided herein may be used to access a broad range of compounds, including aromatic compounds, heteroaromatic compounds, amino acids, nucleotides, and synthetic compounds.
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Page/Page column 26
(2011/08/08)
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- Unprecedented directing group ability of cyclophanes in arene fluorinations with diaryliodonium salts
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For the first time it is shown that exceptionally electron-rich arene rings can be fluorinated exclusively during the reductive elimination reactions of diaryliodonium fluorides. The 5-methoxy[2.2]paracyclophan-4-yl directing group simultaneously reduces unproductive aryne chemistry and eliminates ligand exchange reactions by a combination of steric and electronic effects. Use of the cyclophane directing group permits an unprecedented degree of control in fluorination reactions of diaryliodonium salts.
- Graskemper, Joseph W.,Wang, Bijia,Qin, Linlin,Neumann, Kiel D.,Dimagno, Stephen G.
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scheme or table
p. 3158 - 3161
(2011/08/06)
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- Regiospecific reductive elimination from diaryliodonium salts
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(Figure Presented) Out-of-plane steric bulk furnished by a cyclophane substituent on iodine(III) strongly destabilizes the transition state in the reductive elimination from diaryliodonium salts and leads to regiochemical control (dubbed SECURE), as is demonstrated by computational and experimental studies. This approach should be general for high-valent maingroup and transition metal ions. X=N3, OAc, PhO, CF3CH2O, SCN, PhS.
- Wang, Bijia,Graskemper, Joseph W.,Qin, Linlin,DiMagno, Stephen G.
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supporting information; experimental part
p. 4079 - 4083
(2010/08/07)
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- Anomalous Hydrolysis Behaviour of Paracyclophanediazonium Salts: a New Route to Bridged Benzobarrelenes
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The hydrolysis of diazotized 5-amino-paracyclophane and anti-4-amino-(1,4)naphthalenoparacyclophane gives products having a barrelene structure, presumably via an aryne mechanism.
- Mori, Nobuo,Takemura, Tetsuo,Tsuchiya, Kazahiko
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p. 575 - 576
(2007/10/02)
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