The Difluoromethylated Organogold(III) Complex cis-[Au(PCy3)(4-F-C6H4)(CF2H)(CI)]: Preparation, Characterization, and Its C(sp2)-CF2H Reductive Elimination

被引：19

作者：

Liu, Shuanshuan ^{[1
]}

Kang, Kai ^{[2
]}

Liu, Shihan ^{[3
]}

Wang, Decai ^{[1
]}

Wei, Ping ^{[1
]}

Lan, Yu ^{[3
,4
]}

Shen, Qilong ^{[2
]}

机构：

[1] Nanjing Tech Univ, Biotechnol & Pharmaceut Engn, Nanjing 210009, Jiangsu, Peoples R China

[2] Chinese Acad Sci, Univ Chinese Acad Sci, Shanghai Inst Organ Chem, Key Lab Organofluorine Chem,Ctr Excellence Mol Sy, 345 Lingling Rd, Shanghai 200032, Peoples R China

[3] Chongqing Univ, Sch Chem & Chem Engn, Chongqing 400030, Peoples R China

[4] Zhengzhou Univ, Coll Chem & Mol Engn, Zhengzhou 450001, Henan, Peoples R China

来源：

ORGANOMETALLICS | 2018年 / 37卷 / 21期

基金：

中国国家自然科学基金;

关键词：

PALLADIUM-CATALYZED DIFLUOROMETHYLATION; OXIDATIVE ADDITION; ORGANIC-SYNTHESIS; GOLD COMPLEXES; BOND-FORMATION; C-H; FLUORINE; PD; TRIFLUOROMETHYLATION; REACTIVITY;

D O I：

10.1021/acs.organomet.8b00579

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The preparation of the difluoromethylated organogold(III) complex cis-[Au(PCy3)(4-F-C6H4)(CF2H)(Cl)] (3) and its Ar-CF2H reductive elimination are described. In the presence of 1.0 equiv of AgSbF6 or AgPF6, compound 3 underwent a quantitative Ar-CF2H reductive elimination in less than 1.0 min at 25 degrees C, while the lack of silver salt resulted in Ar-CF2H reductive elimination from complex 3 in 1,1,2,2-tetrachloroethane (CCl2HCCl2H) after 80 min at 115 degrees C to afford the elimination product p-F-PhCF2H (4) and (Cy3P)Au(Cl) in quantitative yields. On the basis of the mechanistic studies of the kinetics of the reaction and DFT calculation, a concerted Ar-CF2H bond-forming pathway for the Ar-CF2H reductive elimination from organogold(III) complex 3 is proposed.

引用

页码：3901 / 3908

页数：8

共 67 条

[11] Pd-Catalyzed Difluoromethylation of Vinyl Bromides, Triflates, Tosylates, and Nonaflates
Chang, Dalu
Gu, Yang
Shen, Qilong
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2015, 21 (16) : 6074 - 6078
[12] Transition-Metal-Catalyzed Difluoromethylation, Difluoromethylenation, and Polydifluoromethylenation Reactions
Chen, Bo
Vicic, David A.
[J]. ORGANOMETALLIC FLUORINE CHEMISTRY, 2015, 52 : 113 - 141
[13] The Palladium-Catalyzed Trifluoromethylation of Aryl Chlorides
Cho, Eun Jin
Senecal, Todd D.
Kinzel, Tom
Zhang, Yong
Watson, Donald A.
Buchwald, Stephen L.
[J]. SCIENCE, 2010, 328 (5986) : 1679 - 1681
[14] Crabtree RH, 2014, ORGANOMETALLIC CHEMISTRY OF THE TRANSITION METALS, 6TH EDITION, P1, DOI 10.1002/9781118788301
[15] Synthesis, Characterization, and Unique Catalytic Activities of a Fluorinated Nickel Enolate
Doi, Ryohei
Kikushima, Kotaro
Ohashi, Masato
Ogoshi, Sensuke
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (09) : 3276 - 3282
[16] Active trifluoromethylating agents from well-defined copper(I)-CF3 complexes
Dubinina, Galyna G.
Furutachi, Hideki
Vicic, David A.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (27) : 8600 - +
[17] Structure of Bis(trifluoromethyl)cuprate and Its Role in Trifluoromethylation Reactions
Dubinina, Galyna G.
Ogikubo, Junichi
Vicic, David A.
[J]. ORGANOMETALLICS, 2008, 27 (23) : 6233 - 6235
[18] Stoichiometric and Catalytic Aryl-Perfluoroalkyl Coupling at Tri-tert-butylphosphine Palladium(II) Complexes
Ferguson, Devin M.
Bour, James R.
Canty, Allan J.
Kampf, Jeff W.
Sanford, Melanie S.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (34) : 11662 - 11665
[19] Catalysis for fluorination and trifluoromethylation
Furuya, Takeru
Kamlet, Adam S.
Ritter, Tobias
[J]. NATURE, 2011, 473 (7348) : 470 - 477
[20] Generation of Hydrofluoronickelacycles from Trifluoroethylene and Ni(0): Ligand Effects on Regio-/Stereoselectivity and Reactivity
Giffin, Kaitie A.
Pua, Lorraine A.
Piotrkowski, Sarah
Gabidullin, Bulat M.
Korobkov, Ilia
Hughes, Russell P.
Baker, R. Tom
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (11) : 4075 - 4086

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