- Unnatural α-Amino Acid Synthesized through α-Alkylation of Glycine Derivatives by Diacyl Peroxides
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We have developed a protocol for catalyst- and additive-free α-alkylation reactions of glycine derivatives with diacyl peroxides, which proceed by a pathway involving addition of alkyl radicals to imine intermediates. The diacyl peroxide substrate acts as both alkylation agent and oxidizing agent, which means it is atom-economical. It was applied to various glycine derivatives, dipeptides, and a 3,4-dihydroquinoxalin-2(1H)-one derivative and could be carried out on a gram scale, indicating its utility for late-stage functionalization.
- Tian, Hao,Xu, Wentao,Liu, Yuxiu,Wang, Qingmin
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supporting information
p. 5005 - 5008
(2020/07/04)
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- Radical alkylation of C(sp3)-H bonds with diacyl peroxides under catalyst-free conditions
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Herein, we describe a protocol for alkylation reactions of C(sp3)-H bonds with diacyl peroxides by means of a process involving cross-coupling between an alkyl radical and an α-Aminoalkyl radical. The mild, catalyst-And additive-free conditions make this protocol superior to previously reported C(sp3)-H alkylation strategies. The protocol was applied to 1,2,3,4-Tetrahydroisoquinolines and a tetrahydro-β-carboline derivative and could be carried out on a gram scale, indicating its utility for the alkylation of late-stage synthetic intermediates.
- Tian, Hao,Xu, Wentao,Liu, Yuxiu,Wang, Qingmin
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supporting information
p. 14813 - 14816
(2019/12/24)
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- Towards targeting anticancer drugs: Ruthenium(II)-arene complexes with biologically active naphthoquinone-derived ligand systems
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Anticancer active metal complexes with biologically active ligands have the potential to interact with more than one biological target, which could help to overcome acquired and/or intrinsic resistance of tumors to small molecule drugs. In this paper we present the preparation of 2-hydroxy-[1,4]-naphthoquinone-derived ligands and their coordination to a RuII(η6-p-cymene)Cl moiety. The synthesis of oxime derivatives resulted in the surprising formation of nitroso-naphthalene complexes, as confirmed by X-ray diffraction analysis. The compounds were shown to be stable in aqueous solution but reacted with glutathione and ascorbic acid rather than undergoing reduction. One-electron reduction with pulse radiolysis revealed different behavior for the naphthoquinone and nitroso-naphthalene complexes, which was also observed in in vitro anticancer assays.
- Kubanik, Mario,Kandioller, Wolfgang,Kim, Kunwoo,Anderson, Robert F.,Klapproth, Erik,Jakupec, Michael A.,Roller, Alexander,S?hnel, Tilo,Keppler, Bernhard K.,Hartinger, Christian G.
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p. 13091 - 13103
(2016/09/04)
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- KINETICS OF ADDITION OF THE ETHYL RADICALS TO FLUOROETHYLENES IN HEPTANE AND ISOOCTANE
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The thermal decomposition of propionyl peroxide in heptane and isooctane was used as a source of free ethyl radicals for kinetic investigations.The rate constants for the addition of C2H5. to ethylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, and tetrafluoroethylene in relation to the rate constants for the abstraction of a hydrogen atom from heptane at 65 deg C are 52.3, 24.0, 10, 84, and 1000 respectively.For ethylene, vinyl fluoride, and trifluoroethylene the relative addition rate constants were also determined in isooctane (178, 78, and 252).Itwas calculated that for the CH3., C2H5., and CF3. radicals the hydrogen abstraction rate from heptane is 3.3, 3.2, and 2.2 times higher respectively than from isooctane.In the investigated systems ethyl radicals exhibit stronger nucleophilic character than methyl radicals.
- Zhuravlev, M. V.,Serov, S. I.,Sass, V. P.,Sokolov, S. V.
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p. 1754 - 1757
(2007/10/02)
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- Safe diacyl peroxide solution compositions
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A safe peroxide solution composition consisting essentially of a diacyl peroxide having 1-5 carbon atoms in each aliphatic group and an aliphatic hydrocarbon, ketone, ester, ether, or alcohol characterized by a vapor pressure substantially that of the peroxide. Example: Equal parts by weight of diacetyl peroxide and ethyl butyl ketone.
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