Professor Zhu Shifa research group of South China University of Technology: transition metal catalyzed efficient conversion of Alkynes

The coordination of the lead metal can activate the unsaturated carbon bond effectively The transition metal catalyzed efficient conversion of unsaturated hydrocarbons has become an important research field in organic chemistry Different types of cyclic compounds can be synthesized by transition metal catalyzed addition of unsaturated hydrocarbons These new reaction methods are of great significance for the synthesis of natural products and bioactive molecules In recent years, Professor Zhu Shifa's research group of South China University of technology has made a series of research progress in the field of transition metal catalyzed efficient conversion of alkynes Brief introduction of Professor Zhu Shifa's research group Professor Zhu Shifa's research group was founded in 2009 The main research direction of the research group is "efficient conversion of unsaturated hydrocarbons" Alkyne is an important chemical basic raw material, and the efficient conversion of alkyne is an important way to achieve molecular diversity Zhu Shifa's research group has been carrying out systematic research on the efficient conversion of alkynes catalyzed by transition metals for many years, mainly based on the basic concept of green chemistry, adopting the series reaction strategy for the high active reaction intermediates (such as onium salt, metal carbene, 1, 3-dipoles, alkenyl metal species, o-methylene benzoquinone) were selectively captured, and a series of characteristic synthesis methods were developed The research group now has 1 postdoctoral student, 5 doctoral students and 9 master students At present, the research group is in the rising stage of development We need to recruit several postdoctors (pay interview) At the same time, we also welcome students who love organic chemistry to join the research group! Profile of Professor Zhu Shifa Zhu Shifa, Professor, doctoral supervisor In June 2001, he graduated from the school of chemistry and chemical engineering of Hunan University In the same year, he was admitted to the Shanghai Institute of organic science of the Chinese Academy of Sciences His tutor was Zhu Shizheng, a researcher In June 2006, he received a doctorate in science from the Shanghai Institute of organic science of the Chinese Academy of Sciences In September of the same year, he went to the United States and successively engaged in postdoctoral research in Syracuse University and University of South Florida In May 2009, he joined the school of chemistry and chemical engineering of South China University of technology as an "overseas excellent talent" In 2010, it was selected into the "new century excellent talents support plan of the Ministry of education", in 2014, it was supported by the "National Natural Science Foundation excellent youth fund", in 2016, it was selected into the "young and middle-aged leading talents of science and technology innovation" of the Ministry of science and technology, and in 2017, it was selected into the national "ten thousand talents plan" leading talents of science and technology innovation More than 70 SCI papers have been published in J am Chem SOC., angel Chem Int ed., chem and other magazines, and more than 10 Chinese invention patents have been applied for It has undertaken the National Natural Science Fund, Guangdong Natural Science Fund, key R & D program subproject of the Ministry of science and technology, 973 self selected project and other projects Frontier research achievements: in recent years, transition metal catalyzed intramolecular carbonyl nucleophilic addition of alkynes has attracted more and more researchers' attention and been widely used in the construction of functional compounds There are many active intermediates involved in this reaction, and many series reactions can take place under different conditions According to Baldwin's rule, there are three different cyclization modes, namely, 5-endo-dig, 5-exo-dig and 6-endo-dig Different cyclization processes can obtain different five membered or six membered ring intermediates, such as alkenyl metal species, pyranes, metal carbenes or pyracarbenes / 1,3-dipoles Zhu Shifa research group of South China University of technology has carried out systematic research on the intramolecular nucleophilic addition reaction of alkyne carbonyl compounds In 2018, he was invited to publish a review on Chem, and introduced in detail the development status of this kind of reaction in recent ten years (CHEM 2018, Doi: 10.1016/j.champr.2018.02.001, Dr Chen Lianfen and Dr Chen Kai are the co first authors of this review) Figure 1 Transition metal catalyzed intramolecular carbonyl nucleophilic addition of alkynes (source: Chem) In 2013, Zhu Shifa's research group first reported the series Diels alder / Diels alder reaction between o-alkynylacetophenone and norbornene catalyzed by NHC AuCl / selectfluor In the first step, 6-endo-dig cyclization took place under the action of gold catalyst, and the intermediate of benzoisopyranoate and norbornene reacted with Diels alder to obtain the secondary intermediate of onium ion, and then 1,4-elimination to obtain the key intermediate o-methylbenzoquinone (o-qdm) The o-qdm intermediate can react with the second molecule norbornene again to form a rigid molecule with a unique sector framework (chem EUR J 2013, 19, 4695) After that, through further research, the author also extended the reaction substrate from the more special norbornene to the common aryl olefins and alkylalkenes and alkynes (org BIOMOL Chem 2014, 12, 4104-4111; J org Chem 2014, 79, 6113-6122; adv.synth Catalyst 2016, 358, 2684-2691) When conjugated 1,3-butadiene is used as olefin substrate in the above catalytic system, the biomimetic synthesis of high tension tricyclic [3.2.1.0] octane skeleton can be realized in one step (chem EUR J., 2014, 20, 2425) Figure 2 The generation and capture of o-qdm intermediates "selective hydrolysis of non terminal alkynes" is one of the challenging topics in the field of organic chemistry After alkyne hydrolysis, a new carbonyl group and a new active methylene group are produced The new carbonyl group and active methylene group can often undergo further chemical transformation However, for the non terminal alkynes, the hydrolysis process is usually less selective, which leads to the application of non terminal alkynes in organic synthesis is limited Based on the carbonyl oxygen transfer strategy, Zhu Shifa's research group successfully realized the selective hydrolysis of non terminal alkynes through the nucleophilic attack of onium ion intermediates by water, and based on this, carried out a series of water assisted series reactions, and synthesized a variety of multi ring systems (Fig 3) (angel W Chem Int ed 2016, 55, 2587; Angel W chem Int ed 2015, 54 , 9414; Org Lett 2017 , 19 , 4540; Adv Synth.Catal 2017 , 359 , 2924; Chem Commun 2015 , 51 ,5530）。 Fig 3 Selective hydrolysis of non terminal alkynes under the catalysis of transition metals, alkyne carbonyl compounds are good precursors of carbofuran metal In 2016, Zhu Shifa's research group reported the first case of donor / donor carbene asymmetric transfer reaction produced by non diazo strategy In this system, rhodium complex of chiral carboxylate is used as catalyst, alkyne ketone is used as carbene precursor, and explosive donor / donor diazo is avoided as carbene precursor The products of C-H insertion and cyclopropanation are obtained with near quantitative yield and excellent enantioselectivity and non enantioselectivity (angel Chem Int ed., 2016, 55, 8452) In addition, based on the furan metal carbene intermediate, they carried out a series of carbene transfer reactions with conjugated alkyne ketone as the precursor, including X-H insertion, cyclopropanation, Buchner reaction and azacyclopropane reaction (org Lett 2014, 16, 4472-4475; org Lett 2016, 18, 1322-1325; org Lett 2016, 18, 5208-5211) Fig 4 Professor Zhu Shifa's research group, based on the series reaction of metal carbene intermediates, also carried out the corresponding research work in combination with alkyne chemistry guided by the active natural product molecules Recently, they used the Claisen rearrangement strategy in series to produce highly active p-benzoquinone intermediates, and then developed a new method to synthesize the multi substituted salicylaldehyde skeleton through the capture of intermolecular nucleophiles This method can be used to construct all substituted benzene rings with high oxidation state in a simple and efficient way It has the advantages of no catalyst, high atom economy, high step economy and gram level preparation Fig 5 Based on the above methodology, they also used the product obtained by this method for the total synthesis of natural products and their analogues In the linear step of 15 steps, the total yield of 3.7% completed the total synthesis of gossypol, a natural product with multiple biological activities The same route can also be used for the effective synthesis of hemigossypol and gossypol analogues At present, this work has been published online in German Journal of Applied Chemistry (angel.chem.int.ed 2018, 57, DOI: 10.1002/anie.201801612) Figure 6 Total synthesis of hemigossypol, gossypol and their analogues (source: angelw Chem Int ed.) the above research work has been greatly supported by NSFC, Ministry of science and technology, Ministry of education, Department of science and technology of Guangdong Province, Guangzhou Science and technology innovation Commission, South China University of Technology and other units in scientific research funds 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, chembeango app, 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.