研究综述/Summary

本人的主要学术贡献主要分成两个部分：1. 基于一氧化碳的C1化学：针对目前钯催化C-H键酰胺羰基化反应中广泛存在的二级胺导致催化剂失活的问题，使用三级胺C-N断键作为胺源，从而高效构建多种酰胺键。这之后，本人又通过使用镍催化体系以及氯甲酸酯作为CO源，成功实现了烷基酮类衍生物的合成。该策略避免了钯催化羰基化反应中存在的一系列科学问题。2.       生物催化体系研究：我们根据乳酸消旋酶中的金属辅因子结构仿生合成了三种镍pincer模型，并证明了其具备乳酸消旋酶的功能。我们根据这类模型研究生物体中乳酸消旋酶催化的机制。本人目前为止共合作发表文章21篇，影响因子总和接近200。其中一作文章11篇，包括3篇Angew. Chem. Int. Ed.，1篇Acc. Chem. Res.，5篇Chem. Commun.，1篇Org. Chem. Front以及1篇Sci. China Chem.等。本人的h-index为11，文章总引用超过1100，其中他引超过1000。

 

My works will be divided into two parts: 1. C1 chemistry based on CO: it remains a great challenge to achieve Pd-catalyzed C-H bond aminocarbonylation due to the decomposition of catalysis caused by the strong coordination and reducibility of secondary amines. To solve this problem, the tertiary amines are used as the amine source through C-N bond activation in our protocol, giving various amides as the products. On the other hand, using Ni catalysis, we are able to prepare a wide range of both symmetric and asymmetric dialkyl ketones from two molecules of alkyl halides and ethyl chloroformate (ClCOOEt), a safe and easy to handle CO source, avoiding the shortcomings of Pd-catalyzed carbonylation. 2.       biomimetic catalysis: A novel nickel pincer cofactor was recently discovered in lactate racemase. Here we report three synthetic nickel pincer complexes which are both structural and functional models of the pincer cofactor in lactate racemase. DFT computations suggest that the ipso-carbon of the pyridinium pincer ligands acts as a hydride acceptor for lactate isomerization, whereas an organometallic pathway involving Ni-mediated β-H elimination is less favored. During my PhD and Postdoc period, I have published more than 21 papers at international renowned journals (Angew. Chem. Int. Ed., Acc. Chem. Res., Chem. Rev., Chem. Commun., Org. Chem. Front., Chem. Eur. J.). Among them, there are 11 first-author/corresponding-author papers (3 papers at Angew. Chem. Int. Ed., 1 paper at Acc. Chem. Res., 5 papers at Chem. Commun. and 1 paper at Org. Chem. Front.). My h-index is 11 and total citation is about 1100.

发表文章/Publications

1)  R. Shi, X. Hu*, From Alkyl Halides to Ketones: Nickel-Catalyzed Reductive Carbonylation Utilizing Ethyl Chloroformate as a Carbonyl Source, Angew. Chem. In. Ed. 2019, 58, 7454-7458. IF：12.257.

 

2)  R. Shi, M. D. Wodrich, H. Pan, R. Scopelliti, X. Hu*, Functional Models of the Nickel Pincer Nucleotide Cofactor of Lactate Racemase, Angew. Chem. In. Ed. 2019, 58, 16869-16872. IF：12.257.

 

3)  R. Shi, L. Lu, H. Zhang, B. Chen, Y. Sha, C. Liu, A. Lei*, Palladium/Copper-Catalyzed Oxidative C-H Alkenylation /N-Dealkylative Carbonylation of Tertiary Anilines, Angew. Chem. In. Ed. 2013, 52, 10582-10585. IF：12.257.

 

4)  R. Shi, Z. Zhang, X. Hu*, Nickamine and Analogous Nickel Pincer Catalysts for Cross-Coupling of Alkyl Halides and Hydrosilylation of Alkenes, Acc. Chem. Res. 2019, 52, 1471-1483. IF：21.661.

 

5)  R. Shi#, H. Zhang#, L. Lu, P. Gan, Y. Sha, H. Zhang, Q. Liu, M. Beller*, A. Lei*, (E)-α, β-Unsaturated Amides from Tertiary Amines, Olefins and CO via Pd/Cu-Catalyzed Aerobic Oxidative N-Dealkylation, Chem. Commun. 2015, 51, 3247-3250. IF：6.164.

 

6)  R. Shi, L. Lu, H. Xie, J. Yan, T. Xu, H. Zhang, X. Qi, Y. Lan*, A. Lei*, C8–H Bond Activation vs. C2–H Bond Activation: from Naphthyl Amines to Lactams, Chem. Commun. 2016, 52, 13307-13310. IF：6.164.

 

7)  R. Shi, H. Niu, L. Lu, A. Lei*, Pd/Cu-Catalyzed Aerobic Oxidative Aromatic C-H Bond Activation/ N-Dealkylative Carbonylation towards the Synthesis of Phenanthridinones, Chem. Commun. 2017, 53, 1908-1911. IF：6.164.

 

8)  R. Shi, F. Liao, H. Niu, A. Lei*, Selective formation of phthalimides from amines, aldehydes and CO by Pd-catalyzed oxidative C-H aminocarbonylation, Org. Chem. Front. 2018, 5, 1957-1961. IF：5.07.

 

9)  F. Liao#, R. Shi#, Y. Sha, J. Xia, W. Liao, A. Lei*, Pd/Cu-catalyzed dual C-H bond carbonylation towards the synthesis of fluorazones, Chem. Commun. 2017, 53, 4354-4357. IF：6.164.

 

10)  Y. Liu, L. Xue, B. Shi, F. Bu, D. Wang, L. Lu, R. Shi*, A. Lei*, Catalyst-free electrochemical decarboxylative cross-coupling of N-hydroxyphthalimide esters and N-heteroarenes towards C(sp3)–C(sp2) bond formation, Chem. Commun. 2019, 55, 14922-14925. IF：6.164.

 

11)  Z. Chen, F. Lu, F. Yuan, J. Sun, Linyu. Du, Z. Li, M. Gao*, R Shi*, Aiwen Lei*, Photocatalysis Decarboxylative Coupling between α-oxocarboxylic Acids and Alkenes, Sci. China Chem. 2019, 62, 1497–1500. IF：6.085

 

12)  H. Zhang, R. Shi, P. Gan, C. Liu, A. Ding, Q. Wang, A. Lei*, Palladium-Catalyzed Oxidative Double C-H Functionalization/ Carbonylation for the Synthesis of Xanthones, Angew. Chem. In. Ed. 2012, 51, 5204-5207. IF：12.257.

 

13)  H. Zhang, R. Shi, A. Ding, L. Lu, B. Chen, A. Lei*, Transition-Metal-Free Alkoxycarbonylation of Aryl Halides, Angew. Chem. Int. Ed. 2012, 51, 12542-12545. IF：12.257.

 

14)  L. Lu, R. Shi, A. Lei*, Oxidation-induced Formal C-H Bond Activation and Functionalization, Trends in Chemistry, Under revision.

 

15)  L. Lu, R. Shi, L. Liu, Z. Yan, F. Lu, A. Lei*, Oxidative Alkane C-H Alkoxycarbonylation, Chem. Eur. J. 2016, 41, 14484-14488. IF：5.160.

 

16)  H. Niu, L. Lu, R. Shi, C. Chiang*, A. Lei*, Catalyst-free N-Methylation of Amines Using CO2, Chem. Commun. 2017, 53, 1148-1151. IF：6.164.

 

17)  W. Hao, J. Tian, W. Li, R. Shi, Z. Huang, A. Lei*, Nickel-Catalyzed Oxidative C-H/N-H Isocyanide Insertion: An Efficient Synthesis of Iminoisoindolinone Derivatives, Chem. Asian J. 2016, 11, 1664-1667. IF：3.698.

 

18)  L. Lu, D. Cheng, Y. Zhan, R. Shi, C. Chiang, A. Lei*, Metal-free radical oxidative alkoxycarbonylation and imidation of alkanes, Chem. Commun. 2017, 53, 6852-6855. IF：6.164.

 

19)  J. Wen, S. Tang, F. Zhang, R. Shi, A. Lei*, Palladium/Copper Co-catalyzed Oxidative C-H/C-H Carbonylation of Diphenylamines: A Simple Way to Access Acridones, Org. Lett. 2017, 19, 94-97. IF：6.492.

 

20)  C. Liu, J. Yuan, S. Tang, W. Li, R. Shi, M. Gao, A. Lei*, Oxidative Coupling between Two Hydrocarbons: An Update of Recent C-H Functionalizations, Chem. Rev. 2015, 22, 12138-12204. IF：54.301.

 

21)  L. Zeng, H. Li, J. Hu, D. Zhang, J. Hu, P. Peng, S. Wang, R. Shi, J. Peng, C. Pao, J. Chen, J. Lee, H. Zhang, Y. Chen*, A. Lei*, Electrochemical Oxidative Aminocarbonylation of Termianl Alkynes, Nat. Catal. 10.1038/s41929-020-0443-z.