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    Home > Green catalytic synthesis team of Shaanxi Normal University: Iron catalyzed anti martensitic hydroamination and hydroamidation of allyl alcohol

    Green catalytic synthesis team of Shaanxi Normal University: Iron catalyzed anti martensitic hydroamination and hydroamidation of allyl alcohol

    • Last Update: 2019-09-05
    • Source: Internet
    • Author: User
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    Lead hydroamination is an important method to construct C-N bond In the reaction, the N-H unit of primary amine or secondary amine is added to C-C double bond or triple bond to form new nitrogen compounds, which has high atomic economy Recently, the green catalytic synthesis team of Shaanxi Normal University reported the anti mahalanolamine and hydroamidation of allyl alcohol catalyzed by iron The reaction achieved a good synergistic catalytic cycle of iron catalysis and amine catalysis, and selectively realized the anti mahalanolamine reaction of allyl alcohol, with a wide range of substrates, as many as 76 examples, and also the first anti mahalanolamine reaction of amide and allyl alcohol Professor Xiao Jianliang and Professor Wang Chao are the corresponding authors of the article, and Ma Wei, a doctoral student, is the first author of the article Relevant research results are published on J am Chem SOC (DOI: 10.1021 / JACS 9b05221) Fig 1 anti mahalanolamine and hydroamidation of allyl alcohol catalyzed by iron (source: J am Chem SOC.) brief introduction of green catalytic synthesis team of Shaanxi Normal University chief professor of green catalytic synthesis team of Shaanxi Normal University: Professor Xiao Jianliang, 1960 Born in Fuping, Shaanxi Province, he has obtained bachelor's degree, master's degree and doctor's degree respectively in Northwest University, Beijing Institute of petroleum and chemical sciences and University of Alberta, Canada At present, he is a professor in the Department of chemistry, Liverpool University, UK In the past decade, the green catalytic synthesis team has been committed to the research of new catalytic reactions A series of new catalysts and systems have been developed for organic synthesis reactions, which provide a new method for the green of synthetic chemistry At present, research progress has been made in several research directions, such as photocatalytic reaction, asymmetric hydrogenation, hydrogen borrowing reaction and manganese catalytic oxidation reaction (angelw.chem.int.ed 2019, 58, 10528; angelw.chem.int.ed 2019, 58, 6380; angelw.chem.int.ed 2018, 57, 1968; ACS catalyst 2019, 9, 4441; ACS catalyst 2017, 7, 1831; chem SCI 2016, 7, 3399 )。 Professor Wang Chao and doctoral student Ma Wei Wang Chao, Professor of Shaanxi Normal University, once won Pfizer R & dschorarship, 2010 national excellent self funded overseas student scholarship, 2016 Shaanxi science and technology star title Presided over and completed a number of NSFC projects He has published more than 50 papers in important influential journals at home and abroad, and obtained many authorized patents At present, the research interests are mainly focused on metal catalyzed dehydrogenation and hydrogen borrowing reactions, selective conversion of biomass platform molecules and green chemistry Ma Wei was admitted to Ningxia Normal University in 2007 and received his Bachelor of Science Degree in 2011 In the same year, he was admitted to Shaanxi Normal University to study for master's degree, under the guidance of Professor Xiao Jianliang and Professor Xue Dong In 2015, he became a doctoral student, under the guidance of Professor Xiao Jianliang and Professor Wang Chao, he was engaged in the research of alkylation by hydrogen Research achievements: in the past 20 years, the amination of alkynes and alkenes has been widely used in the synthesis of fine chemicals, drugs and agricultural chemicals There is a problem of selectivity in the hydroamination of olefins There are two kinds of products, one is the addition product of martensite and the other is the addition product of anti martensite Recently, the research group has developed the hydrogen amination and hydrogen amidation of amines / amides with allyl alcohol catalyzed by cheap metal iron catalyst (FE PNP), and realized the green synthesis of selective anti martensitic addition product γ - aminoalcohols (Figure 2) Fig 2 iron catalyzed hydroamination and hydroamidation of allyl alcohol (source: J am Chem SOC.) based on the research work of hydrogen borrowing reaction reported by the research group (chem EUR J 2018, 24, 13118; chem Commun 2017, 53, 3051; chem EUR J 2017, 23, 14445; chem SCI 2016, 7, 3399), the author envisages dehydrogenation of allyl alcohol under the action of iron catalyst to generate the intermediate of unsaturated allylaldehyde; it then selectively reacts with amine to generate β - aminoaldehydes by Mike addition reaction; β - aminoaldehydes can be reduced by Fe-H intermediate to generate γ - aminoalcohols (as shown in Fig 2) The feature of the reaction design is that the product of anti - mahalanobism can be effectively generated and the product of mahalanobism can be avoided Through the selection of reaction conditions, the author found that the use of catalyst 3 (structure shown in Fig 2) can selectively realize the anti mahalanolamine of allyl alcohol, and alkali and non proton solvent have a great influence on the activity of the reaction Under the optimal reaction conditions, allyl alcohol compounds are used as alkylation reagents to carry out hydroamination reaction with different amines (as shown in Fig 3) Firstly, the hydroamination of various secondary and primary aromatic amines with allyl alcohol 5A was studied The reaction of secondary aromatic amines with allyl alcohol has a good effect, and the substrate containing Dinh functional group can selectively generate the product of Dialkylation (6O); the yield of primary aromatic amines is lower than that of secondary aromatic amines, and the reaction needs a slightly higher catalyst amount and a higher temperature (6p-6s) When aliphatic amines are used as the substrate, the catalyst will be poisoned due to the strong coordination effect In this catalytic system, the hydroamination of aliphatic amines with allyl alcohol can be well realized For the reaction of aliphatic primary amines with 5A, the product of Dialkylation (8h - 8L) was selectively generated It is worth noting that the chirality of the chiral substrate can be well maintained in this reaction, and the original chirality configuration of the substrate will not change (such as 8e, 8F) Amides participate in the hydroamination reaction, which is also called the hydroamination reaction Because of the weak nucleophilic, the amides often have poor reactivity in the hydroamination reaction Up to now, there is no report about the hydroamidation of allyl alcohol and amide The catalytic system has general applicability to amide compounds, including primary amide, secondary amide and heterocyclic amide (10a - 10L) The author also investigated the reactions of allylic alcohols with amines at different positions The reaction sites were all at the γ position of allylic alcohols, and the yield was good At the same time, the reaction also has good functional group tolerance The reaction selectively generates the target product 11C, and there is no by-product of double bond reduction It is worth noting that when 3-butene-1-ol is used as the substrate, the product is the same as that when 2-butene-1-ol is used as the substrate, which indicates that there may be a double bond migration process in the reaction process When cyclopropenol was used as the substrate, the reaction could produce trans addition product 11i with high selectivity Another highlight of some products (source: J am Chem SOC.) reported in Fig 3 is that the reaction can carry out good functionalization of chiral amino acid esters to generate new chiral γ - hydroxy amino acid esters (Fig 4, 12a-12h) Natural products and drug molecules can also be modified to obtain new target molecules (12i-12n) For example, several common commercial drugs, such as cytisine, Troxipide, amoxapine, fluoxetine, rolipram, duloxetine, can well modify N-H units to form corresponding γ - Hydroxylamine products, and the yield is good Fig 4 functional studies of amino acid esters, natural products and drug molecules (source: J am Chem SOC.) in terms of mechanism, the author designed various experiments to verify the synergistic catalytic cycle process of iron catalysis and amine catalysis Combined with mechanism experiments and related literatures, the author proposed possible reaction mechanism: firstly, catalyst 3 generates active catalyst intermediate 17 under the activation of nabhet 3; secondly, allyl alcohol 5A generates negative hydrogen intermediate 18 and acrolein 19 through the dehydrogenation of 17 in the presence of alkali; then 19 and 20 condense to form active Michael receptor 21, 21 and 20 After the addition of AZA Michael, the intermediate 22 is obtained, and the intermediate 22 is hydrolyzed to unsaturated intermediate 23; finally, the intermediate 23 is reduced to target product 24 under the action of negative hydrogen intermediate 18, and the active catalyst 17 is released (Fig 5) The intermediate 21 of imine cation was detected in the process of reaction, which indicated that the addition step of AZA Michael may be the decisive step of the reaction Meanwhile, the activity of primary amine in the reaction is relatively low, which can indirectly prove this view Because the primary amine and allylaldehyde form imine neutral molecule, its activity is weaker than imine positive ion intermediate 21 Fig 5 possible reaction mechanism (source: J am Chem SOC.) to sum up, the author developed a method of iron catalyzed hydroamination and hydroacylation of allyl alcohol The catalytic system has good anti martensitic selectivity, mild reaction conditions, wide range of substrates and good functional group tolerance At the same time, the catalytic system can retain the stereoscopic configuration of the chiral substrate, and can modify amino acid esters, natural products and drug molecules, and high allyl alcohol is also feasible in this reaction The mechanism study shows that the reaction is carried out through two collaborative catalytic cycles, namely, the dehydrogenation / hydrogenation process catalyzed by Fe PNP complex and Michael addition process promoted by amine substrate as organic catalyst The catalytic reaction has expanded the hydroamination reaction and provided a new way for the synthesis of amines Nowadays, people and scientific research have been paid more and more attention in the economic life China has ushered in the "node of science and technology explosion" Behind the progress of science and technology is the work of countless scientists In the field of chemistry, in the context of the pursuit of innovation driven, international cooperation has been strengthened, the influence of Returned Scholars in the field of R & D has become increasingly prominent, and many excellent research groups have emerged in China For this reason, CBG information adopts the 1 + X reporting mechanism CBG information website, chembeangoapp, chembeango official micro blog, CBG information wechat subscription number and other platforms jointly launch the column of "people and scientific research", approach the representative research groups in China, pay attention to their research, listen to their stories, record their demeanor, and explore their scientific research spirit.
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