- Iron-Catalysed Remote C(sp3)?H Azidation of O-Acyl Oximes and N-Acyloxy Imidates Enabled by 1,5-Hydrogen Atom Transfer of Iminyl and Imidate Radicals: Synthesis of γ-Azido Ketones and β-Azido Alcohols
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In the presence of a catalytic amount of iron(III) acetylacetonate [Fe(acac)3], the reaction of structurally diverse ketoxime esters with trimethylsilyl azide (TMSN3) afforded γ-azido ketones in good to excellent yields. This unprecedented distal γ-C(sp3)?H bond azidation reaction went through a sequence of reductive generation of an iminyl radical, 1,5-hydrogen atom transfer (1,5-HAT) and iron-mediated redox azido transfer to the translocated carbon radical. TMSN3 served not only as a nitrogen source to functionalise the unactivated C(sp3)?H bond, but also as a reductant to generate the catalytically active FeII species in situ. Based on the same principle, a novel β-C(sp3)?H functionalisation of alcohols via N-acyloxy imidates was subsequently realised, leading, after hydrolysis of the resulting ester, to β-azido alcohols, which are important building blocks in organic and medicinal chemistry.
- Torres-Ochoa, Rubén O.,Leclair, Alexandre,Wang, Qian,Zhu, Jieping
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supporting information
p. 9477 - 9484
(2019/05/21)
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- Photoredox-Catalyzed Decarboxylative Alkylation of Silyl Enol Ethers to Synthesize Functionalized Aryl Alkyl Ketones
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Photoredox-catalyzed decarboxylative alkylation of silyl enol ethers has been developed. Diverse functionalized aryl alkyl ketones were afforded in modest to good yields using N-(acyloxy)phthalimide as an easy access alkyl radical source under mild and operationally simple conditions. The excellent performance of drug molecules such as fenbufen and indomethacin and naturally occurring carboxylic acids such as stearic acid and dehydrocholic acid further demonstrated the practicability of the reaction.
- Kong, Weiguang,Yu, Changjiang,An, Hejun,Song, Qiuling
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p. 349 - 352
(2018/01/28)
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- Preparation, Properties and Crystal Structures of New Nickel(II) Complexes of 1,2-Asymmetrically Substituted Dithiolenes for Third-order Non-linear Optical Applications
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Three new nickel(II) complexes of 1-alkyl-2-phenyl asymmetrically substituted dithiolenes 1=CR2S)2> (R1 = Ph; R2 = n-Bu, cyclopentylmethyl or 4-pentylcyclohexyl) have been prepared and their electrochemic
- Hill, Callum A. S.,Charlton, Adam,Underhill, Allan E.,Malik, K. M. Abdul,Hursthouse, Michael B.,et al.
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p. 587 - 594
(2007/10/02)
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