付亮
Office: Building No.5 408
Lab: Building No.5 410-411
Phone: (0086) 15212758128
E-mail: liangfu-chem@mail.ahnu.edu.cn
The Fu group homepage: https://www.x-mol.com/groups/Fu
Prof. Dr. Liang Fu obtained his Bachelor degree in Applied Chemistry in 2009 from Huazhong Agricultural University. In the same year, he began his graduate studies under the supervision of Prof. Dr. Wen-Jing Xiao at Central China Normal University. After receiving his Master degree in Organic Chemistry in 2012, he left China to start his doctoral studies under the guidance of Prof. Dr. Meike Niggemann at RWTH Aachen University in Germany. In 2016, he conducted short-term postdoctoral research in the laboratory of Prof. Dr. Karl Anker Jørgensen at Aarhus University in Denmark. In 2017, he moved to a postdoctoral position with Prof. Dr. Guosheng Liu at Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences (CAS), where his research interest centered on copper-catalyzed radical relay for asymmetric radical transformations (ARTs). In 2020, he started to work independently at Anhui Normal University.
Research Interest
The development of highly efficient and environmentally benign methodologies for direct functionalization of alkynes considered as one of the most fundamental transformations in modern organic synthesis is of great importance. During my Ph.D studies in the Niggemann group at RWTH Aachen University, aluminum or calcium-catalyzed electrophilic cyclizations of alkynes via vinyl cations have been investigated. In these reactions, trisubstituted highly reactive vinyl cations were generated by the nucleophilic addition of alkynes to carbocations produced from secondary alcohols. Subsequently, the vinyl cations could be intercepted by a tethered aromatic nucleophile, leading to the formation of all-carbon tetrasubstituted olefins (Chem. Eur. J. 2015, 21, 6367-6370). Alternatively, the highly reactive vinyl cations could undergo an unprecedented 1,3-aryl shift to yield a more stable allylic carbocation, by which a net insertion of internal alkynes into a C(SP2)-C(SP3) σ bond under transition metal-free conditions has been demonstrated (Chem. Eur. J. 2017, 23, 12158-12161). Furthermore, in-depth mechanistic studies on the 1,3-aryl migration have also been conducted by experiments and DFT calculations (Chem. Eur. J. 2017, 23, 12184-12189).
More recently, as a postdoctor under the guidance of Prof. Dr. Guosheng Liu at Shanghai Institute of Organic Chemistry (SIOC), the direct functionalization of alkynes via a radical process has been disclosed on the basis of a copper-catalyzed radical relay strategy for asymmetrical radical transformations (ARTs) developed by the Liu group. First, the enantioselective alkynylation of benzylic radicals generated by CF3 radical addition to styrenes has been developed (J. Am. Chem. Soc. 2018, 140, 10965-10969). Second, the enantioselective alkynylation of benzylic radicals produced by abstracting hydrogen atoms at the benzylic position of alkylarenes with N-centered radicals has been realized (J. Am. Chem. Soc. 2020, 142, 12493-12500). Lastly, detailed mechanistic studies on the key step for an enantioselective combination of chiral (Box)CuII-alkynyl species and benzylic radicals have been demonstrated by experiments and DFT calculations.
Over the last decade, functionalization of alkynes via a radical process, serving as a powerful tool for efficient synthesis of multi-substituted alkenes, has been extensively investigated. In these studies, a key vinyl radical intermediate was involved, which prompted us to survey a possible radical strategy for the concise synthesis of vinylarene atropisomers from aryl-substituted vinyl radicals generated through radical addition to arylacetylenes bearing two different ortho substituents. Based on this hypothesis, a novel asymmetric radical strategy for the straightforward synthesis of atropisomerically chiral vinylarenes has been established, proceeding through copper-catalyzed atroposelective cyanation/azidation of aryl-substituted vinyl radicals. The asymmetric capture of the highly reactive aryl-substituted vinyl radicals with chiral L*Cu(II) cyanide or azide species is a key step for the formation of C(SP2)− CN/C(SP2)−N3 bonds in an atroposelective and (E)-selective manner (J. Am. Chem. Soc. 2023, 145, 13476-13483).
Journal Publications
1. L. Fu; X. Chen; W. Fan; P. Chen; G. Liu* “Copper-Catalyzed Asymmetric Functionalization of Vinyl Radicals for the Access to Vinylarene Atropisomers”. J. Am. Chem. Soc. 2023, 145, 13476-13483.
2. Z. Hu; L. Fu; P. Chen; W. Cao*; G. Liu* “Enantioselective Intermolecular Aminoalkynylation of Styrenes via Copper-Catalyzed Radical Relay”. Org. Lett. 2021, 23, 129-134.
3. S. Zhou; G. Zhang; L. Fu; P. Chen; Y. Li*; G. Liu* “Copper-Catalyzed Asymmetric Cyanation of Alkenes via Carbonyl-Assisted Coupling of Alkyl-Substituted Carbon-Centered Radicals”. Org. Lett. 2020, 22, 6299-6303.
4. G. Zhang; S. Zhou; L. Fu; P. Chen; Y. Li*; J. Zou*; G. Liu* “Asymmetric Coupling of Carbon-Centered Radicals Adjacent to Nitrogen: Copper-Catalyzed Cyanation and Etherification of Enamides”. Angew. Chem. Int. Ed. 2020, 59, 20439-20444.
5. L. Fu; Z. Zhang; P. Chen; Z. Lin*; G. Liu* “Enantioselective Copper-Catalyzed Alkynylation of Benzylic C-H Bonds via Radical Relay”. J. Am. Chem. Soc. 2020, 142, 12493-12500 (Highlighted by X-MOL https://www.x-mol.com/news/458867 and Synfacts 2020, 16, 1082).
6. L. Fu; S. Greßies; P. Chen; G. Liu* “Recent Advances and Perspectives in Transition Metal-Catalyzed1,4-Functionalizations of Unactivated 1,3-Enynes for the Synthesis of Allenes”. Chin. J. Chem. 2020, 38, 91-100.
7. G. Zhang; L. Fu; P. Chen; J. Zou*; G. Liu* “Proton-Coupled Electron Transfer Enables Tandem Radical Relay for Asymmetric Copper-Catalyzed Phosphinoylcyanation of Styrenes”. Org. Lett. 2019, 21, 5015-5020.
8. L. Fu; S. Zhou; X. Wan; P. Chen; G. Liu* “Enantioselective Trifluoromethylalkynylation of Alkenes via Copper-Catalyzed Radical Relay”. J. Am. Chem. Soc. 2018, 140, 10965-10969 (Highlighted by Synfacts 2018, 14, 1168).
9. X. Qi; C. Chen; C. Hou; L. Fu; P. Chen; G. Liu* “Enantioselective Pd(II)-Catalyzed Intramolecular Oxidative 6-endo Aminoacetoxylation of Unactivated Alkenes”. J. Am. Chem. Soc. 2018, 140, 7415-7419.
10. C. Chen; Y. Luo; L. Fu; P. Chen; Y. Lan*; G. Liu* “Palladium-Catalyzed Intermolecular Ditrifluoromethoxylation of Unactivated Alkenes: CF3O-Palladation Initiated by Pd(IV)”. J. Am. Chem. Soc. 2018, 140, 1207-1210.
11. L. Fu; H. Damsen; M. Niggemann* “A Vinyl Cation-Induced 1,3-Aryl Shift”. Chem. Eur. J. 2017, 23, 12158-12161.
12. M. Niggemann*; L. Fu; H. Damsen “Taming a Vinyl Cation with a Simple Al(OTf)3 Catalyst to Promote C-C Bond Cleavage”. Chem. Eur. J. 2017, 23, 12184-12189.
13. L. A. Leth; F. Glaus; M. Meazza; L. Fu; M. K. Thøgersen; E. A. Bitsch; K. A. Jørgensen* “Decarboxylative [4+2] Cycloaddition by Synergistic Palladium and Organocatalysis”. Angew. Chem. Int. Ed. 2016, 55, 15272-15276.
14. L. Fu; M. Niggemann* “Calcium-Catalyzed Carboarylation of Alkynes”. Chem. Eur. J. 2015, 21, 6367-6370 (Selected as hot paper and the cover picture of the corresponding issue).
15. V. J. Meyer; L. Fu; F. Marquardt; M. Niggemann* “Calcium-Catalyzed Cycloisomerization of Enynes”. Adv. Synth. Cat. 2013, 355, 1943-1947.
16. L. Fu; C.-J. Yao; N.-J. Chang; J.-R. Chen; L.-Q. Lu*; W.-J. Xiao* “Oxidative Cross-Esterification of Dithiolanes with Alcohols through a Cross-Dehydrogenative Coupling (CDC)/Deprotection Sequence”. Org. Biomol. Chem. 2012, 10, 506-508.
17. Y.-Q. Zou; L.-Q. Lu; L. Fu; N.-J. Chang; J. Rong; J.-R. Chen; W.-J. Xiao* “Visible-Light-Induced Oxidation/[3+2] Cycloaddition/Oxidative Aromatization Sequence: A Photocatalytic Strategy To Construct Pyrrolo[2,1-a]isoquinolines”. Angew. Chem. Int. Ed. 2011, 50, 7171-7175.
18. J.-R. Chen*; L. Fu; Y.-Q. Zou; N.-J. Chang; J. Rong; W.-J. Xiao* “Pyrrolidinyl-sulfamide Derivatives as a New Class of Bifunctional Organocatalysts for Direct Asymmetric Michael Addition of Cyclohexanone to Nitroalkenes”. Org. Biomol. Chem. 2011, 9, 5280-5287.
19. J.-R. Chen*; Y.-J. Cao; Y.-Q. Zou; F. Tan; L. Fu; X.-Y. Zhu; W.-J. Xiao* “Novel Thiourea-amine Bifunctional Catalysts for Asymmetric Conjugate Addition of Ketones/Aldehydes to Nitroalkenes: Rational Structural Combination for High Catalytic Efficiency”. Org. Biomol. Chem. 2010, 8, 1275-1279.
20. J.-R. Chen*; Y.-Q. Zou; L. Fu; F. Ren; F. Tan; W.-J. Xiao* “Highly Enantioselective Michael Addition of Aldehydes to Nitroolefins Catalyzed by Primary Amine Thiourea Organocatalysts”. Tetrahedron 2010, 66, 5367-5372.