Research group of Professor He liangnian of Nankai University: pauson khand reaction of rhodium catalyzed formic acid as carbonyl source -- a new way to indirectly utilize CO2

With people's continuous attention to environmental issues such as greenhouse effect, the research on the basis and application development of "CO 2 turning waste into treasure" based on the concept of green chemistry is of great significance and application prospect Among them, Professor He liangnian of the school of chemistry of Nankai University has made outstanding contributions to the chemical transformation methodology and resource utilization of CO2 Recently, the research group has made new breakthroughs in this field (greenchem., 2019, DOI: 10.1039/c8gc03933j) Introduction to Professor He liangnian's research group professor he liangnian's research group was founded in 2003 Now there are 18 researchers, including 1 Professor, 3 full-time teachers, 2 postdoctoral students, 3 doctoral students and 9 master's students Relying on the National Key Laboratory of elemental organic, Nankai University, the research group took the lead in the research of CO 2 chemistry, and made a series of innovative achievements in high value utilization strategy of CO 2 and catalytic reaction in environmentally friendly media Professor he liangnian, Professor He liangnian, professor and doctoral supervisor of School of chemistry, Nankai University, devoted to green chemistry teaching and research From 2014 to 2018, it was selected into the list of highly cited Chinese scholars, from 2014 to 2016, it was selected into the "top 1% highly cited Chinese scholars list" of the Royal Chemical Society of the United Kingdom, the "carbon dioxide chemical transformation reaction research" won the third prize of Natural Science in Tianjin in 2014, and the "castor oil derivative base oil synthesis and Application Research" won the third prize of military science and technology progress in 2017 In 2015, he was awarded the pioneer post of Tianjin education system; in 2018, he was awarded the eighth mentor award of Nankai University Participate in and undertake projects such as National Natural Science Fund, national basic research "12th Five Year Plan" science and technology support project, Tianjin Natural Science Fund key project, national key R & D plan, etc In 2013, he participated in organizing the 246th annual meeting of American Chemical Society "materials and technologies for CO2 capture, sequence and conversion" In 2015, he convened and presided over the branch of "carbon dioxide capture and utilization" of the Eighth National Environmental Chemistry Conference (as one of the conveners) On June 11-15, 2017, he made an invitation report at Gordon Research Conference on CCUs: CO 2 chemistry: combination of carbon capture and subsequence conversion In 2018, he was invited to organize and edit the album of carbon dioxide chemistry in the Journal of "Chinese Chemistry" In 2018, it organized and hosted the 49th session of the 43rd International Conference on Coordination Chemistry: carbon dioxide catalytic conversion Conference (July 30-August 4, 2018, Sendai, Japan), and made an invitation report entitled "carbondioxide chemistry: carbon capture and in situ catalysis" On November 5-6, 2018, the conference report "CO 2 chemistry on a way towards climate neutral synthetic chemistry" was made at the International Conference on green chemistry, which was highly praised On November 7-9, 2018, he was invited to work in the max plan institute for chemical energy conversion on the title of "CO 2 chemistry: institu catalysis for CO 2 upgrading" Brief introduction to Dr Lang Xiandong, studied in Zaozhuang College since 2006, entered Qufu Normal University in 2009, and obtained a Bachelor of Science Degree in 2011 He liangnian and Li Zhengming were admitted to Nankai University in 2012 They were engaged in green chemistry research In 2015 and 2018, they obtained master's degree and doctor's degree from Nankai University respectively They were interested in the research of carbonylation involving carbon dioxide and carbon monoxide substitutes They published 9 academic papers with the first author They were 8 consecutive in the period of master's degree and master's degree He has won various scholarships, and made three reports in domestic academic conferences Frontier research achievements: rhodium catalyzed formic acid as carbonyl source, pauson khand reaction -- a new way to indirectly utilize CO 2, pauson khand reaction refers to the transition metal catalyzed intermolecular or intramolecular carbon double bond, triple bond and co cyclization reaction Cyclopentenone is a kind of important structural unit widely existing in natural products and bioactive molecules However, most of these reactions require CO gas which is colorless, odorless, highly toxic and inconvenient to transport and store, and often need to use high temperature and high pressure resistant devices Therefore, the development of CO substitutes with low toxicity and convenient transportation and storage has gradually attracted extensive attention of researchers Common co substitutes include metal carbonyl compounds, acyl chloride, formic acid, oxalic acid, etc Among them, formic acid can be obtained not only by reduction of greenhouse gas CO2, but also by oxidation of biomass, which is regarded as an ideal, green and environmental co substitute Recently, the research team of Professor He liangnian of Nankai University developed a new strategy of pauson khand reaction with formic acid as the precursor of CO (Fig 1), which realized the indirect utilization of CO 2 Finally, cyclopentenone compounds were obtained in the yield of 49-86% At the same time, the strategy was successfully applied to the synthesis of heterocyclic molecules with medicinal value The reaction process is simple and can avoid the direct use of Toxic Gas Co the relevant results are published on green chem (DOI: 10.1039 / c8gc03933j) Fig 1 A new strategy of pauson khand reaction with formic acid as co precursor (source: Green chem.) firstly, the author selected 2-allyl-2 - (3-phenyl-2-propynyl) - diethyl malonate as template substrate, [RhCl (CO) 2] 2 as catalyst, n-butyl ether as solvent, acetic anhydride as additive, and realized Formic acid as formic acid under the reaction conditions of 130 ℃ and 24 h The pauson khand reaction of CO precursor and the screening of a series of formates showed that the real carbonyl source in the reaction was formic acid Then the author selected the optimal reaction conditions through a series of experiments: with 2 mol% of [RhCl (COD) 2] 2 as catalyst, 0.75 mmol of acetic anhydride as additive, at 130 ℃, 0.5 mmol of alkyne and 1.5 mmol of formic acid obtained the optimal yield after 24 hours of reaction (Fig 2) Fig 2 Optimization of reaction conditions (source: Green chem.) then, the author investigated the applicability of the catalytic system with carbon atom and oxygen atom as the bridge chain of 1,6-enyne substrate, and obtained the corresponding cyclopentenone product in medium to high yield (Fig 3) The results show that this method has a wide range of substrate applicability Fig 3 The pauson khand reaction with rhodium catalyzed formic acid (source: Green chem.) in addition, the results of the enlarged gram scale experiment (Fig 4) and the evaluation of the catalytic efficiency (Table 1) also show the high efficiency of the catalytic system in the synthesis of cyclopentenone skeleton compounds using formic acid as a co substitute Fig 4 Gram scale experiment of asuson khand reaction involving formic acid (source: Green chem.) table 1 Evaluation of catalytic efficiency (source: Green chem.) next, the author also found that the system is also suitable for heterocyclic pauson khand reaction, And the reaction can obtain heterocyclic compounds with medicinal value in good yield (Fig 5), which further expands the application scope of the existing methods Figure 5 Heterocyclic pauson khand reaction with formic acid (source: Green chem.) based on the literature and experimental results, the author proposed the possible reaction mechanism (Figure 6) Firstly, formic acid interacts with acetic anhydride to form mixed anhydrides, which are decomposed to form CO and acetic acid Subsequently, CO is coordinated with rhodium catalyst to form intermediate B B then coordinated with the double bond and triple bond of the substrate, and activated the substrate to form intermediate C C is oxidized and added to form intermediate D at last, D is transferred and inserted by CO and eliminated by reduction to form final product Figure 6 Possible reaction mechanism (source: Green chem.) Summary: formic acid can be used as a bridge molecule for reducing CO 2 to CO for rhodium catalyzed pauson khand reaction (Figure 7) It is proved that the system has high efficiency and yield, and avoids the use of toxic CO as carbonyl source It is convenient to operate, practical and has a wide application prospect Figure 7 Review of previous reports on the pauson khand reaction (source: Green Chem) in which formic acid is a bridge molecule from CO 2 to CO: Professor He liangnian, Nankai University Research Group: selective N-methylation and n-formylation of amines by CO2, hydrosilanes regulated by copper catalytic ligands 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, chembeangoapp, chembeango official microblog, CBG wechat subscription number and other platforms jointly launch the column of "people and scientific research", approach the domestic representative research group, pay attention to their research, listen to their stories, record their demeanor, and explore their scientific research spirit.