Photoenzymatic Generation of Unstabilized Alkyl Radicals: An Asymmetric Reductive Cyclization
Flavin-dependent "ene"-reductases can generate stabilized alkyl radicals when irradiated with visible light; however, they are not known to form unstabilized radicals. Here, we report an enantioselective radical cyclization using alkyl iodides as precursors to unstabilized nucleophilic radicals. Evidence suggests this species is accessed by photoexcitation of a charge-transfer complex that forms between flavin and substrate within the protein active site. Stereoselective delivery of a hydrogen atom from the flavin semiquinone to the prochiral radical formed after cyclization provides high levels of enantioselectivity across a variety of substrates. Overall, this transformation demonstrates that photoenzymatic catalysis can address long-standing selectivity challenges in the radical literature.
Clayman, Phillip D.,Hyster, Todd K.
supporting information
p. 15673 - 15677
(2020/10/18)
Palladium-Catalyzed C(sp3)-H Nitrooxylation with tert-Butyl Nitrite and Molecular Oxygen
Herein, we report a Pd(II)-catalyzed nitrooxylation of unactivated methyl C(sp3)-H bonds using commercial available and easily manageable tert-butyl nitrite as the precursor of ONO2 radical under aerobic conditions. Environmentally benign molecular oxygen is used to initiate the generation of active radical reactant; it is also used as the terminal oxidant. A broad range of nitrooxylated aliphatic carboxamides were prepared in moderate to good yields under mild conditions.
Han, Ye-Qiang,Li, Bo,Shi, Bing-Feng,Yang, Xu
supporting information
p. 9719 - 9723
(2020/12/21)
Unactivated C(sp3)-H hydroxylation through palladium catalysis with H2O as the oxygen source
A novel palladium catalyzed hydroxylation of unactivated aliphatic C(sp3)-H bonds was successfully developed. Different from conventional methods, water serves as the hydroxyl group source in the reaction. This new reaction demonstrates good reactivity and broad functional group tolerance. The C-H hydroxylated products can be readily transformed into various highly valuable chemicals via known transformations. Based on experimental and theoretical studies, a mechanism involving the Pd(ii)/(iv) pathway is proposed for this hydroxylation reaction.
Developing Pd(II) catalyzed double sp3 C-H alkoxylation for synthesis of symmetric and unsymmetric acetals
An effective Pd(II) catalyzed double unactivated C(sp3)-H alkoxylation has been developed to prepare both symmetric and unsymmetric acetals. This new reaction demonstrates good functional group tolerance, excellent reactivity, and high yields. A variety of novel acetals can be readily accessed via this new method. (Chemical Equation Presented).
Zong, Yu,Rao, Yu
supporting information
p. 5278 - 5281
(2015/01/09)
Effiziente Synthese neuer 2-Cycloalk(en)yl-propansaeure-Derivate - mittlere und grosse Ringe als Bioisostere von Alkylphenylresten?
Synthesis of Oxa- and Thia- analogs of Bicycloalkanes
A general and convenient synthetic approach of a variety of oxa- and thia- analogs of bicycloalkanes is described.This is illustrated by the synthesis of a series of 2-oxa(IIa-d)- and 2-thia(IIa-d)- analogs of bicyclooctane(I) on one hand and 4-oxa(Va-d)- and 4-thia(VIa-d)- analogs of bicyclodecane(IV) on the other.The analogs of I and IV are obtained by cyclohydration of the diols XIX and XXI respectively usung dil.H2SO4 or DMSO.The diols in turn are prepared starting from the keto acids VII.On the otherhand, treatment of di-tosylates XX and XXII of XIX and XXI with Na2S in refluxing ethanol affords the respective 2-thia(III)- and 4-thia(VI)- analogs of I and IV systems.The formation of oxolans(II) via oxidative cyclisation of the cycloalkaneethanols(XXIII) with lead tetraacetate is also described.
Rao, R. R.,Sarkar, Rina,Bhattacharya, Sukla,Mukherjee, M. N.
p. 939 - 946
(2007/10/02)
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