Dual Roles for Potassium Hydride in Haloarene Reduction: CSNAr and Single Electron Transfer Reduction via Organic Electron Donors Formed in Benzene

被引:37
作者
Barham, Joshua P. [1 ,2 ]
Dalton, Samuel E. [1 ,2 ]
Allison, Mark [1 ]
Nocera, Giuseppe [1 ]
Young, Allan [1 ]
John, Matthew P. [2 ]
McGuire, Thomas [3 ]
Campos, Sebastien [2 ]
Tuttle, Tell [1 ]
Murphy, John A. [1 ]
机构
[1] Univ Strathclyde, Dept Pure & Appl Chem, 295 Cathedral St, Glasgow G1 1XL, Lanark, Scotland
[2] GlaxoSmithKline Med Res Ctr, Gunnels Wood Rd, Stevenage SG1 2NY, Herts, England
[3] AstraZeneca, Med Chem, Oncol, IMED Biotech Unit, 319 Milton Rd, Cambridge CB4 0WG, England
基金
英国工程与自然科学研究理事会;
关键词
C-H ARYLATION; PARAMAGNETIC-RESONANCE SPECTROSCOPY; NUCLEOPHILIC AROMATIC-SUBSTITUTION; MOLECULAR-ORBITAL METHODS; METAL-FREE ARYLATION; UNACTIVATED ARENES; TERT-BUTOXIDE; KINETIC APPLICATIONS; RADICAL REACTIONS; ARYL BROMIDES;
D O I
10.1021/jacs.8b07632
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Potassium hydride behaves uniquely and differently than sodium hydride toward aryl halides. Its reactions with a range of haloarenes, including designed 2,6-dialkylhaloarenes, were studied in THF and in benzene. In THF, evidence supports concerted nucleophilic aromatic substitution, CSNAr, and the mechanism originally proposed by Pierre et al. is now validated through DFT studies. In benzene, besides this pathway, strong evidence for single electron transfer chemistry is reported. Experimental observations and DFT studies lead us to propose organic super electron donor generation to initiate BHAS (base-promoted homolytic aromatic substitution) cycles. Organic donor formation originates from deprotonation of benzene by KH; attack on benzene by the resulting phenylpotassium generates phenylcyclohexadienylpotassium that can undergo (i) deprotonation to form an organic super electron donor or (ii) hydride loss to afford biphenyl. Until now, BHAS reactions have been triggered by reaction of a base, MOtBu (M = K, Na), with many different types of organic additive, all containing heteroatoms (N or O or S) that enhance their acidity and place them within range of MOtBu as a base. This paper shows that with the stronger base, KH, even a hydrocarbon (benzene) can be converted into an electron-donating initiator.
引用
收藏
页码:11510 / 11518
页数:9
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