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沈其龙

作者: 时间:2020-04-08 点击数:

沈其龙

研究员

电话:021-54925197

电子邮箱:shenql@mail.sioc.ac.cn

联系地址:上海市零陵路345号,邮编:200032

Shanghai Institute of Organic Chemistry, 345 Lingling Lu, Shanghai,200032

简介:(学习工作经历)中文和英文

教育背景

1992年9月-1996年7月南京大学环境科学与工程系,本科毕业

1996年9月-1999年7月上海有机化学研究所,获理学硕士学位

2000年9月-2002年7月美国麻省大学Dartmouth分校,获理学硕士学位

2002年9月-2007年9月美国耶鲁大学,获博士学位

工作经历

1999年8月-2000年8月,上海有机化学研究所,研究助理

2007年10月-2010年3月,美国伊利诺伊斯大学香槟分校化学系博士后

2010年4月-至今,上海有机化学研究所,课题组长

发表论文

73. A Key Intermediate in Copper‐Mediated Arene Trifluoromethylation [nBu4N][Cu(Ar)(CF3)3]: Synthesis, Characterization and C(sp2)‐CF3Reductive Elimination

Lu, Z.-H.; Liu, H.; Liu, S.-Y.; Leng, X.-B.; Lan, Y.; Shen, Q.Angew. Chem. Int. Ed.2019,58, 8510

72.Synthesis and Reactivity of α‐Cumyl Bromodifluoromethanesulfenate: Application to the Radiosynthesis of [18F]ArylSCF3

Wu, J.; Zhao, Q.-C.; Wilson, T. C.; Verhoog, S.; Lu, L.; Gouverneur, V.; Shen, Q.Angew. Chem. Int. Ed.2019,58, 2413

71.Facilitating the Transmetalation Step with Aryl-Zincates in Nickel-Catalyzed Enantioselective Arylation of Secondary Benzylic Halides

Huang. W.-C.; Hu, M.; Leng, X.-B.; Shen, Q.Nat. Commun.2019,10: 2963, doi: 10.1038/s41467-019-10851-4

70.Trifluoromethyl-substituted selenium ylide: a broadly applicable electrophilic trifluoromethylating reagent

Ge, H.-M.; Shen, Q.Org. Chem. Front.2019,6,2205

69.[Ag(bpy)(PPhtBu2)(OCF3)]: a stable nucleophilic reagent for chemoselective and stereospecific trifluoromethoxylation of secondary alkyl nosylates

Chen, D.-Q.; Lu, L.; Shen, Q.Org. Chem. Front.2019,6,1801

68.Bistrifluoromethylated Organocuprate [Ph4P]+[Cu(CF3)2]-: Synthesis, Characterization and Its Application for Trifluoromethylation of Activated Heteroaryl Bromides, Chlorides and Iodides

Liu, H.; Shen, Q.Org. Chem. Front.2019,10, 2324

67.Cobalt-Catalyzed Cross-Coupling of Lithium (Hetero)Aryl Zinates with Heteroaryl Chlorides and Bromides

Liu, S.-S.; Huang, W.-C.; Wang, D.-C.; Wei, P.; Shen, Q.Org. Chem. Front.2019,10,2630

66.2-[(1,3-Dihydro-1,3-dioxo-2H-isoindol-2-yl)thio]-2,2-difluoroacetate

Shen, Q.eEROS2019,accepted.

65.Copper-Catalyzed Carbene Insertion into the Sulfur–Sulfur Bond of RS–SCF2H/SCF3under Mild Conditions

Hong. X.; Lu, L.; Shen, Q.Synlett2019,30, 1602.

64.The Difluoromethylated Organogold(III) complescis-[Au(PCy3)(4-F-C6H4)(CF2H)(Cl)]: Preparation, Characterization, and Its C(sp2)-CF2H Reductive Elimination

Liu, S.-S.; Kang, K.; Liu, S.-H.; Wang, D.-C.; Wei, P.; Lan, Y.; Shen, Q.Organometallics,2018,37, 3901

63.Carbon-Selective Difluoromethylation of Soft Carbon Nucleophiles with Difluoromethylated Sulfonium Ylide

Zhu, J.-S.; Zheng, H.-L.; Xue, X.-S.; Xiao, Y.-S.; Liu, Y.-F.; Shen, Q.Chin. J. Chem.2018,36, 1069

62.Pd-Catalyzed Difluoromethylthiolation of Aryl Chlorides, Bromides and Triflates

Wu, J.; Lu, C.-H.; Lu, L. Shen, Q.Chin. J. Chem.2018,36, 1031

61.Radical fluoroalkylthiolation of aldehydes with PhSO2SRf(Rf= CF3, C2F5, CF2H or CH2F): a general protocol for the preparation of fluoroalkylthioesters

Xu, B.; Li, D.-Z.; Lu, L.; Wang, D.-C.; Hu, Y.-H.; Shen, Q.Org. Chem. Front.2018,5, 2163

60.Silver-catalyzed ring-opening difluoromethylthiolation/trifluoromethylthiolation of cycloalkanols with PhSO2SCF2H or PhSO2SCF3

Xu, B.; Wang, D.-C.; Hu, Y.-H.; Shen, Q.Org. Chem. Front.2018,5, 1462

59.Palladium-Catalyzed Difluoromethylation of Aryl Chlorides and Triflates and Its Applications in the Preparation of Difluoromethylated Derivatives of Drug/Agrochemical Molecules

Lu, C.-H.; Lu, H.; Wu, J.; Shen, H. C.; Hu, T.-S.; Gu, Y.-C.; Shen, Q.J. Org. Chem.2018,83, 1077

58.Ligand‐Controlled Copper‐Catalyzed Highly Regioselective Difluoro‐methylation of Allylic Chlorides/Bromides and Propargyl Bromides

Gu, Y.; Lu, C.-H.; Gu, Y.-C.; Shen, Q.Chin. J. Chem.2018,36, 55

57.Monofluoromethyl-Substituted Sulfonium Ylides: Electrophilic Monofluoromethylating

Reagents with Broad Substrate Scopes

Liu, Y.-F.; Lu, L.; Shen, Q.Angew. Chem. Int. Ed.2017,56, 9930

56.Direct Monofluoromethylthiolation with S-(Fluoromethyl) Benzenesulfonothioate

Zhao, Q.-C.; Lu, L.; Shen, Q.Angew. Chem. Int. Ed.2017,56, 11575

55.Enantioselective Construction of Trifluoromethoxylated Stereogenic Centers by a Nickel

Catalyzed Asymmetric Suzuki–Miyaura Coupling of Secondary Benzyl Bromides

Huang, W.-C.; Wan, X.-L.; Shen, Q.Angew. Chem. Int. Ed.2017,56, 11986

54.Palladium-catalyzed difluoromethylation of heteroaryl chlorides, bromides and iodides

Lu, C.-H.; Gu, Y.; Wu, J.; Gu, Y.-C.; Shen, Q.Chem. Sci.2017,8, 4848

53.[[(Ethoxycarbonyl)difluoromethyl]thio]phthalimide: A Shelf-Stable, Electrophilic

Reagent with a Convertible Group for the Synthesis of Diversified Fluoroalkylthiolated

Compounds

Shen, F.; Zhang, P.-P.; Lu, L.; Shen, Q.Org. Lett.2017,19, 1032

52.(1S)-(−)-N-Trifluoromethylthio-2,10- camphorsultam and its derivatives: easily available,

optically pure reagents for asymmetric trifluoromethylthiolation

Zhang, H.; Leng, X.-B.; Wang, X.-L.; Shen, Q.Org. Chem. Front.2017,4, 1051

51.C(sp2)−C(sp2) Reductive Elimination from Well-Defined Diarylgold(III) Complexes

Kang, K.; Liu, S.-S.; Xu, T.; Wang, D.-C.; Leng, X.-B.; Bai, R.-P.; Lan, Y.; Shen, Q.

Orgometallics2017,36, 4727

50.直接三氟甲硫基化试剂及方法的研究进展

Zhang, P.-P.; Lu, L.; Shen, Q.Acta Chim. Sinica2017,75, 744

49.Preparation ofN-Trifluoromethylthiosaccharin: A Shelf- Stable Electrophilic Reagent for

Trifluoromethylthiolation

Zhu, J.-S.; Xu, C.-H.; Xu, C.-F. Shen, Q.Org. Synth.2017,94, 217

48.Direct of Difluoromethylation of Alcohols with an Electrophilic Difluoromethylated Sulfonium

Ylide

Zhu, J.-S.; Liu, Y.-F.; Shen, Q.Angew. Chem.Int. Ed.2016,55, 9050.

47.PhSO2SCF2H: A Shelf-Stable, Easily Scalable Reagent for Radical Difluoromethylthiolation

Zhu, D.-H.; Shao, X.-X.; Hong, X.; Lu, L.; Shen, Q.Angew. Chem.Int. Ed.2016,55, 15807.

46.Palladium-catalyzed difluoromethylthiolation of heteroaryl bromides, iodides, triflates and aryl

iodides

Wu, J.; Liu, Y.-F.; Lu, C.-H.; Shen, Q.Chem. Sci.2016,7, 3757.

45.N‑Trifluoromethylthio-dibenzenesulfonimide: A Shelf-Stable, Broadly Applicable

Electrophilic Trifluoromethylthiolating Reagent

Zhang, P. P.; Li, M.; Xue, X.-S.; Xu, C.-F.; Zhao, Q.-C.; Liu, Y.-F.; Wang, H.-Y.; Guo, Y.-L.;

Lu, L.; Shen, Q.J. Org. Chem.2016,81, 7486.

44.Nucleophilic Trifluoromethylthiolation of Alkyl Chlorides, Bromides and Tosylates

Xu, C.-F.; Chen, Q.-Y.; Shen, Q.Chin. J. Chem.2016,34, 495.

43.Pentafluoroethylbenziodoxole (BIX-C2F5): A Shelf-Stable Reagent for Pentafluoroethylation of

β-Ketoesters and Arylboronic Acids

Zhu, J.-S.; Li, Y.-G.; Ni, C.-F.; Shen, Q.Chin. J. Chem.2016,34, 662.

42.Shelf-Stable Electrophilic Reagents for Trifluoromethylthiolation

Shao, X.-X.; Xu, C.-F.; Lu, L.; Shen, Q.Acc. Chem. Res.2015,48, 1227.

41.Copper-Promoted Sandmeyer Difluoromethylthiolation of Aryl and Heteroaryl Diazonium Salts

Wu, J.; Gu, Y.; Leng, X.-B.; Shen, Q.Angew. Chem.Int. Ed.2015,54, 7648.

40.N-Difluoromethylthiophthalimide: A Shelf-Stable Electrophilic Regent for Difluoromethyl- thiolation

Zhu, D.-H.; Gu, Y.; Lu, L.; Shen, Q.J. Am. Chem. Soc.2015,137, 10547.

39.Lewis Acid Mediated Trifluoromethylthio Lactonization/Lactamization

Xu, C.-F.; Shen, Q.Org. Lett.2015,17, 4561

38.Trifluoromethyl-Substituted Sulfonium Ylide: Rh-Catalyzed Carbenoid Addition to Trifluoro- methylthioether

Liu, Y.-F.; Shao, X.-X.; Lu, L.; Shen, Q.Org. Lett.2015,17, 2752

37.Pd-Catalyzed difluoromethylation of Vinyl Bromides, Tosylates and Nonaflates

Chang, D.-L.; Gu, Y.; Shen, Q.Chem.Eur. J.2015,21, 6074.

36.Iron-Catalyzed Markovnikov-Selective Hydrotrifluoromethylthiolation of Unacti-vated Alkenes

Yang, T.; Lu, L.; Shen, Q.Chem.Commun.2015,51, 5479.

35.Structure-Reactivity Relationship of Trifluoromethanesulfenates: Discovery of an Electrophilic Trifluoromethylthiolating Reagent

Shao, X.-X.; Xu, C.-F.; Lu, L.; Shen, Q.J. Org. Chem.2015,80, 3012.

34.Well-Defined, Shelf-Stable (NHC)Ag(CF2H) Complexes for Difluoromethylation

Gu, Y.; Chang, D.-L.; Leng, X.-B.; Gu, Y.-C.; Shen, Q.Organometallics2015,34, 3065

33.BrØnsted acid-catalyzed electrophilic trifluoromethylthiolation of indoles using thermally stable trifluoromethylthiolating reagent

Ma, B.-Q.; Shao, X.-X.; Shen, Q.J. Fluorine Chem.2015,171, 73.

32.Cooperative Dual Palladium/Silver Catalyst for Direct Difluoromethylation of aryl Bromides and Iod-ides

Gu, Y.; Leng, X.-B.; Shen, Q.Nat. Commun.2014,5, 5405

31.Silver-Catalyzed Decarboxylative Trifluoromethylthiolation of Aliphatic Carboxylic Acids in Aqueous Emulsion

Hu, F.; Shao, X.-X.; Zu, D.-H.; Lu, L.; Shen, Q.Angew. Chem. Int. Ed.2014,53, 6105

30.N-Trifluoromethylthiosaccharin: An Easily Accessible, Shelf-Stable, Broadly Applicable Trifluoro- methylthiolating Reagent

Xu, C.-F.; Ma, B.-Q.; Shen, Q.Angew. Chem. Int. Ed.2014,53, 9316

29.Palladium-Catalyzed Trifluoromethylthiolation of Aryl C−H Bonds

Xu, C.-F.; Shen, Q.Org. Lett.2014,16, 2046

28.Nickel-Catalyzed α-Arylation of Zinc Enolates with Polyfluoroarenes via C–F Bond Activation under Neutral Conditions

Yu, D.-H.; Wang, C.-S.; Yao, C.; Shen, Q.; Lu, L.Org. Lett.2014,16, 5544.

27.Copper-Catalyzed Trifluoromethylthiolation of Primary and Secondary Alkylboronic Acids

Shao, X.-X.; Liu, T.-F.; Lu, L.; Shen, Q.Org. Lett.2014,16, 4738

26.Copper-catalyzed Trifluoromethylthiolation of Aryl and Vinyl Boronic Acids with a Shelf-Stable Electrophilic Trifluoromethylthiolating Reagent

Kang, K.; Xu, C.-F.; Shen, Q.Org. Chem. Front.2014,1, 294

25.Chincona Alkaloid-Catalyzed Enantioselective Trifluoromethylthiolation of Oxindoles

Yang, T.; Shen, Q.; Lu, L.Chin. J. Chem.2014,32, 678

24.An Electrophilic Hypervalent Iodine Reagent for Trifluoromethylthiolation

Shao, X.-X.; Wang, X.-Q.; Yang, T.; Long Lu, L. Shen, Q.Angew. Chem. Int. Ed.2013,52, 3457

23.Enantioselective Electrophilic Trifluoromethylthiolation of b-Ketoesters: A Case of Reactivity and Selectivity Bias for Organocatalysis

Wang, X.-Q.; Yang, T.; Cheng, X.-L.; Shen, Q.Angew. Chem. Int. Ed.2013,52, 12860

22.Palladium-Catalyzed Coupling of Polyfluorinated Arenes with Heteroarenes via C-F/C-H Activation

Yu, D.-H.; Lu, L.; Shen, Q.Org. Lett.2013,15, 940

21.Enantioselective Organocatalytic Michael Addition of Nitroalkanes and Other Nucleophiles to β‑Trifluoromethylated Acrylamides

Wen, L.-L.; Yin, L.; Shen, Q.; Lu, L.ACS Catal.2013,3, 502

20.Palladium-Catalyzed Cross-Coupling of Fluorinated Vinyl Chlorides with Terminal Alkynes: A General Protocol to Fluorinated Enynes

Chen, S.; Xu, C.-F.; Lu, L.; Shen, Q.Chin. J. Chem.2013,31, 901

19.A General and Highly Selective Method for the Asymmetric Synthesis of Trifluoromethyl-Substitutedα- andβ-Aminophosphonates

Wang, L.-J.; Shen, Q.; Lu, L.Chin. J. Chem.2013,31, 892.

18.Highly Selective Trifluoromethylation of 1,3-Disubstituted Arenes through Iridium-Catalyzed Arene Borylation

Liu, T.-F.; Shao, X.-X.; Wu, Y.-M.; Shen, Q.Angew. Chem. Int. Ed.2012,51, 540.

17.Copper-Mediated Aerobic Fluoroalkylation of Arylboronic Acids with Fluoroalkyl Iodides at Room Temperature

Qi, Q.-Q.; Shen, Q.; Lu, L.J. Am. Chem. Soc.2012,134, 6548.

16.Bis(perfluoroalkyl) Phosphino-Oxazoline: A Modular, Stable, Strongly π‑Accepting Ligand for Asymmetric Catalysis

Hu, Z.-J.; Li, Y.-G.; Liu, K.; Shen, Q.J. Org. Chem.2012,77, 7957

15.Selective Palladium-Catalyzed C−F Activation Carbon−Carbon Bond Formation of Polyfluoro- aryl Oxazolines

Yu, D.-H.; Shen, Q.; Lu, L.J. Org. Chem.2012,77,1798

14.Preparation of Trifluorostyrenes via Palladium-Catalyzed Coupling of Aryl Boronic Acids with Chloro- and Bromo-Trifluoroethylene

Xu, X.-F.; Chen, S.; Lu, L.; Shen, Q.J. Org. Chem.2012,77, 10314

13.Highly Selective Activation of Vinyl C-S Bond over Aryl C-S Bond in Pd-Catalyzed Coupling of Trifluoromethyl-ated Vinyl Diphenyl Sulfonium Salts. A General Protocol to Trifluoromethylated Alkenes and Dienes

Lin, H.; Dong, X.-C.; Li, Y.-X.; Shen, Q.; Lu, L.Eur. J. Org. Chem.2012, 4675

12.Progresses in Copper-mediated Formation of Trifluoromethylated Arene

Liu, T.-F.; Shen, Q.Eur. J. Org. Chem.2012,6679

11.General and highly efficient fluorinated-N-heterocyclic carbene-based catalysts for the palladium-catalyzed Suzuki-Miyaura reaction

Liu, T.-P.; Zhao, X.-M.; Shen, Q.; Lu, L.Tetrahedron2012,68, 6535

10.Polyfluoroalkylation of 2-Aminothiazoles

Qi, Q.-Q.; Shen, Q.; Lu, L.J. Fluorine Chem.2012,133, 115

9.A Facile Synthetic Route to 2-Trifluromethyl-Substituted Polyfunctionalized Chromenes and Chromones

Wen, L.-L.; Zhang, H.-H.; Lin, L.; Shen, Q.; Lu, L.J. Fluorine Chem.2012,133, 177

8.Transition metal-catalyzed arene trifluoromethylation

Lv, C.-P.; Shen, Q.; Liu, D.Youji Huaxue2012,32, 1380

7.General and highly efficient fluorinated-N-heterocyclic carbene-based catalysts for the palladium

-catalyzed Suzuki-Miyaura reaction

Liu, T.-P.; Zhao, X.-M.; Shen, Q.; Lu, L.Tetrahedron2012,68, 6535

6.Copper-Catalyzed Trifluoromethylation of Aryl and Vinyl Boronic Acids with An Electrophilic Trifluoromethylating Reagent

Liu, T.; Shen, Q.Org. Lett.2011,13, 2342

5.(β-Trifluoromethyl)Vinyl Sulfonium Salts: Preparation and Reactions with Active Methylene

and Methenyl Compounds

Lin, H.; Shen, Q.; Lu, L.J. Org. Chem.2011,76,7359

4.Enantioselective Friedel-Crafts Alkylation of Indoles with Trifluoroethylidene Malonates

by Copper-Bis(Oxazoline) Complexes: Construction of Trifluoromethyl-Substituted Stereogenic Tertiary Carbon Center

Wen, L.; Shen, Q.; Wan, X.; Lu, L.J. Org. Chem.2011,76, 2282

3.Highly Diastereoselective Synthesis of Optically Pure Trifluoromethyl-Substituted Imidazolidine, Oxazolidine and Thiazolidine

Zhang, H.; Shen, Q.; Lu, L.Tetrahedron Lett.2011,52, 349

2.The Recent Development of Organofluorine Chemistry in China: Asymmetric Construction of

Stereogenic Trifluoromethyl-Substituted Carbon Center

Wen, L.; Shen, Q.; Lu, L.Chimia2011,65, 894

1.Polyfluoroalkylation of 2-Aminothiazoles: Unexpected sp3 C-Cl Substitution Under Mild Conditions

Qi, Q.; Shen, Q.; Lu, L.Chinese J. Chem.2011,29, 2681

奖励

·2019, Bayer Investigator Award

·2018, The Roche Chinese Investigator Award

·2015, Asia Core Program Lectureship Award

·2013, Thieme Chemistry Journal Award



研究领域

一、亲电氟烷基试剂的创制及反应研究

新的氟化/氟烷基化试剂开发是有机氟化学研究中永恒的主题,它为化学合成中氟原子及含氟基团的引入提供了有效的手段。发展条件温和、环境友好、使用方便的氟化/氟烷基化试剂是目前氟化学研究的新趋势。沈其龙课题组自2010年起一直致力于发展高效的亲电氟烷基化试剂。

1.在发展具有原创性的新型亲电氟烷硫基氟烷基试剂开展了系统研究,发展了两类共3个亲电三氟甲硫基试剂,其中包括结构独特的三氟甲基次磺酸酯试剂以及目前活性最高的商品化亲电三氟甲硫基糖精试剂,这两个试剂分别被国内外同行称为“吕-沈试剂”(Lu-Shen reagent)与“沈试剂” (Shen Reagent),发展了首例光学活性亲电三氟甲硫基化试剂,发展了可应用于高效合成[18F]标记的三氟甲硫基化芳烃的亲电溴二氟甲硫基化试剂,解决了温和条件下小分子引入三氟甲硫基的难题;发展了首例亲电二氟甲硫基试剂及首例自由基类型二氟甲硫基试剂,为向有机小分子高效引入二氟甲硫基化提供了新方案;发展了首例自由基类型一氟甲硫基试剂。基于该课题组所发展的一系列亲电氟烷硫基化试剂成立了深圳邦奇氟医学材料有限公司。

2.发展了一类基于结构全新的硫/硒叶立德骨架的亲电三氟甲基、二氟甲基和一氟甲基化试剂,其中三氟甲基取代的硒叶立德与目前已知的亲电三氟甲基化试剂活性相当,二氟甲基及一氟甲基取代的硫叶立德试剂是目前活性最高的亲电二氟甲基/一氟甲基化试剂。

金属有机氟化学研究

1.铜介导/催化芳基三氟甲基化反应的关键中间体三价铜络合物的合成及其还原消除反应研究。铜介导芳基卤化物的三氟甲基化反应自1965年McLoughlin and Thrower首次报道以来,已发展成为合成三氟甲基取代的芳烃与杂芳烃的主要方法。对于该反应的机理,一般认为是通过一个三价铜中间体[Ar-CuIII-CF3]发生还原消除而得。另外一类三氟甲基取代的芳基化合物的合成方法是在铜催化下,芳基硼酸和亲核或亲电三氟甲基试剂的反应。机理上,也认为是生成芳基三价铜物种[Ar-CuIII-CF3],随后发生还原消除,得到最终三氟甲基化产物。然而,上述两类反应中的关键中间体[Ar-CuIII-CF3]从未被检测或分离鉴定。我们成功地首次分离了芳基与三氟甲基配位的三价铜络合物nBu4N+[Cu(Ar)(CF3)3],并通过核磁及对其单晶的X-射线衍射对该结构做了表征。该络合物在室温下稳定,在加热条件下以几乎定量的产率发生还原消除得到三氟甲基取代的芳烃。通过对该还原消除的动力学、溶剂效应及自由基捕获基/单电子转移抑制剂的影响,以及DFT理论计算,我们得出结论三价铜络合物nBu4N+[Cu(Ar)(CF3)3]上的还原消除反应是一个协同成键过程 (Angew. Chem. Int. Ed.2019,58, 8510)。利用该还原消除反应过程中生成的一价铜络合物nBu4N+[Cu(CF3)2],该课题组发现该络合物是一个高效的三氟甲基化试剂,可以在CuI作用下与一系列富电子芳基碘化物、活化的杂环溴化物及氯化物反应,以中等产率得到响应的三氟甲基化产物 (Org. Chem. Front.2019,10, 2324)。

2.钯/银协同催化溴/碘代芳烃的二氟甲基化反应。在氟烷基官能团中,二氟甲基性质独特,由于其与羟基及氨基在酸碱性和电性上相似,容易产生分子内以及分子间的氢键等次级相互作用,增强药物分子与酶之间的结合能力,因此药物化学家在设计药物分子结构时通常把二氟甲基当作是羟基及氨基的生物电子等排体。而如何在发展温和条件下向小分子引入二氟甲基是有机氟化学领域研究的难点。本课题组大胆地提出了一个双金属协同催化二氟甲基化的新策略。研究发现,钯催化的卤代芳烃的二氟甲基化反应的难点是把二氟甲基从TMSCF2H转移到金属钯中间体上,我们巧妙了设计了一个稳定的二氟甲基银试剂,该试剂在溶液里可以高效的实现二氟甲基的转金属,得到关键[(DPPF)Pd(Ar)(CF2H)]中间体,从这个关键中间体还原消除就得到二氟甲基取代的芳烃。在理解这个协同催化反应的基元反应的基础上,首次实现了溴代芳烃的二氟甲基化(Nat. Commun.2014, 5, 5405)。






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