3-bromo-4,5-bis(2,3-dibromo-4,5-dihydroxybenzyl)-l,2-benzenediol (1) is a natural bromophenol isolated from the red algae Rhodomela confervoides that exhibits significant inhibition against protein tyrosine phosph...3-bromo-4,5-bis(2,3-dibromo-4,5-dihydroxybenzyl)-l,2-benzenediol (1) is a natural bromophenol isolated from the red algae Rhodomela confervoides that exhibits significant inhibition against protein tyrosine phosphatase 1B (PTP1B). Based on its activity, we synthesized two new synthetic bromophenols and their methoxy derivatives from vanillin using the structure of natural bromophenol 1 as a scaffold. The structures of these bromophenols were elucidated from H NMR, 13C NMR, and high resolution electron ionization mass spectrometry as 2,3-dibromo-1-(2'-bromo-6'-(3",4"-dimethoxybenzyl)- 3 ',4 '-dimethoxybenzyl)-4,5 -dimethoxybenzene (2), 2,3-dibromo- 1 -(2 '-bromo-6'-(2 "-bromo-4",5 "-dimethoxy- benzyl)-3',4'-dimethoxybenzyl)-4,5-dimethoxybenzene (3), 3,4-dibromo-5-(2'-bromo-6'-(2"-bromo-4",5"- dihydroxybenzyl)-3',4'-dihydroxybenzyl)pyrocatechol (4) and 3,4-dibromo-5-(2'-bromo-6'-(3",4"- dihydroxybenzyl)-3',4'-dihydroxybenzyl)pyrocatechol (5). PTP1B inhibition activities of these compounds were evaluated using a colorimetric assay, and compounds 3 and 4 demonstrated interesting activity against PTP1B.展开更多
Selective oxidation with molecular oxygen as the sole oxidant under mild conditions is of crucialimportance for the long‐term sustainable exploitation of available feedstocks and the formation ofrequired intermediate...Selective oxidation with molecular oxygen as the sole oxidant under mild conditions is of crucialimportance for the long‐term sustainable exploitation of available feedstocks and the formation ofrequired intermediates for organic synthesis and industrial processes.Among the developed oxidationprotocols,innovative strategies using hydroxyimide organocatalysts in combination with metallicor metal‐free cocatalysts have attracted much attention because of the good activities andselectivities of such catalysts in the oxo functionalization of hydrocarbons.This method is based onthe reaction using N‐hydroxyphthalimide,which was first reported by Ishii’s group in the1990s.Although the important and wide‐ranging applications of such catalysts have been summarizedrecently,there are no reviews that focus solely on oxidation strategies using multi‐nitroxy organocatalysts,which have interesting properties and high reactivities.This review covers the concisesynthetic methods and mechanistic profiles of known multi‐nitroxy organocatalysts and summarizessignificant advances in their use in efficient aerobic oxidation.Based on a combination of experimentaland theoretical results,guidelines for the future rational design of multi‐nitroxy organocatalystsare proposed,and the properties of various model multi‐nitroxy organocatalysts are predicted.The present overview of the advantages,limitations,and potential applications of multi‐nitroxyorganocatalysts can provide useful tools for researchers in the field of selective oxidation.展开更多
Homogeneous and heterogeneous types of catalysis are frequently considered as separate disciplines or even opposed to each other.In the present work,a new type of mixed het-ero-/homogeneous catalysis was demonstrated ...Homogeneous and heterogeneous types of catalysis are frequently considered as separate disciplines or even opposed to each other.In the present work,a new type of mixed het-ero-/homogeneous catalysis was demonstrated for the case of selective alkylarene oxidation by molecular oxygen.The proposed catalytic system consists of two widely available components:N-hydroxyphthalimide(NHPI,a homogeneous organocatalyst for free-radical chain reactions)and nanosized TiO_(2)(heterogeneous UV-active photoredox catalyst).The interaction of NHPI with TiO_(2) allows for a shift from UV to visible light photoredox activity and generation of phthalimide-N-oxyl(PINO)radicals that diffuse into the solution where NHPI/PINO-catalyzed free-radical chain reaction can proceed without the additional light input providing a fundamental increase in energy efficiency.The NHPI/TiO_(2) ratio controls the selectivity of oxidation affording preferential formation of hydroperoxide or ketone from alkylarene.展开更多
The catalytic performance of a series of cobalt(Ⅱ) hydroxamates (CoL2) and the synergistic catalytic action of the cobalt complexes combined with N-hydroxyphthalimide (NHPI) in the aerobic oxidation of p-xylene to p-...The catalytic performance of a series of cobalt(Ⅱ) hydroxamates (CoL2) and the synergistic catalytic action of the cobalt complexes combined with N-hydroxyphthalimide (NHPI) in the aerobic oxidation of p-xylene to p-toluic acid (PTA) were investigated. The results showed that the existing synergistic action in the catalytic oxidation can shorten the induction period of the radical reaction and improve the yield of PTA.展开更多
基金Supported by the National Major Research Program of China"The Creation for Significant Innovative Drugs"(No.2009ZX09103-148)the Natural Science Foundation of Shandong(No.BS2009YY011)+1 种基金the Natural Science Foundation of Qingdao(No.10-3-4-8-2-JCH)the Program of Qingdao Shinan District(No.2009-HY-2-14)
文摘3-bromo-4,5-bis(2,3-dibromo-4,5-dihydroxybenzyl)-l,2-benzenediol (1) is a natural bromophenol isolated from the red algae Rhodomela confervoides that exhibits significant inhibition against protein tyrosine phosphatase 1B (PTP1B). Based on its activity, we synthesized two new synthetic bromophenols and their methoxy derivatives from vanillin using the structure of natural bromophenol 1 as a scaffold. The structures of these bromophenols were elucidated from H NMR, 13C NMR, and high resolution electron ionization mass spectrometry as 2,3-dibromo-1-(2'-bromo-6'-(3",4"-dimethoxybenzyl)- 3 ',4 '-dimethoxybenzyl)-4,5 -dimethoxybenzene (2), 2,3-dibromo- 1 -(2 '-bromo-6'-(2 "-bromo-4",5 "-dimethoxy- benzyl)-3',4'-dimethoxybenzyl)-4,5-dimethoxybenzene (3), 3,4-dibromo-5-(2'-bromo-6'-(2"-bromo-4",5"- dihydroxybenzyl)-3',4'-dihydroxybenzyl)pyrocatechol (4) and 3,4-dibromo-5-(2'-bromo-6'-(3",4"- dihydroxybenzyl)-3',4'-dihydroxybenzyl)pyrocatechol (5). PTP1B inhibition activities of these compounds were evaluated using a colorimetric assay, and compounds 3 and 4 demonstrated interesting activity against PTP1B.
基金supported by the China Postdoctoral Science Foundation (2014M551746)~~
文摘Selective oxidation with molecular oxygen as the sole oxidant under mild conditions is of crucialimportance for the long‐term sustainable exploitation of available feedstocks and the formation ofrequired intermediates for organic synthesis and industrial processes.Among the developed oxidationprotocols,innovative strategies using hydroxyimide organocatalysts in combination with metallicor metal‐free cocatalysts have attracted much attention because of the good activities andselectivities of such catalysts in the oxo functionalization of hydrocarbons.This method is based onthe reaction using N‐hydroxyphthalimide,which was first reported by Ishii’s group in the1990s.Although the important and wide‐ranging applications of such catalysts have been summarizedrecently,there are no reviews that focus solely on oxidation strategies using multi‐nitroxy organocatalysts,which have interesting properties and high reactivities.This review covers the concisesynthetic methods and mechanistic profiles of known multi‐nitroxy organocatalysts and summarizessignificant advances in their use in efficient aerobic oxidation.Based on a combination of experimentaland theoretical results,guidelines for the future rational design of multi‐nitroxy organocatalystsare proposed,and the properties of various model multi‐nitroxy organocatalysts are predicted.The present overview of the advantages,limitations,and potential applications of multi‐nitroxyorganocatalysts can provide useful tools for researchers in the field of selective oxidation.
文摘Homogeneous and heterogeneous types of catalysis are frequently considered as separate disciplines or even opposed to each other.In the present work,a new type of mixed het-ero-/homogeneous catalysis was demonstrated for the case of selective alkylarene oxidation by molecular oxygen.The proposed catalytic system consists of two widely available components:N-hydroxyphthalimide(NHPI,a homogeneous organocatalyst for free-radical chain reactions)and nanosized TiO_(2)(heterogeneous UV-active photoredox catalyst).The interaction of NHPI with TiO_(2) allows for a shift from UV to visible light photoredox activity and generation of phthalimide-N-oxyl(PINO)radicals that diffuse into the solution where NHPI/PINO-catalyzed free-radical chain reaction can proceed without the additional light input providing a fundamental increase in energy efficiency.The NHPI/TiO_(2) ratio controls the selectivity of oxidation affording preferential formation of hydroperoxide or ketone from alkylarene.
基金supported by the National Natural Science Foundation of China(Grant No.20072025).
文摘The catalytic performance of a series of cobalt(Ⅱ) hydroxamates (CoL2) and the synergistic catalytic action of the cobalt complexes combined with N-hydroxyphthalimide (NHPI) in the aerobic oxidation of p-xylene to p-toluic acid (PTA) were investigated. The results showed that the existing synergistic action in the catalytic oxidation can shorten the induction period of the radical reaction and improve the yield of PTA.