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

[1] [Anonymous], 2009, ORGANOTRANSITION MET
[2] Synthesis, Characterization, and Reactivity of Palladium Fluoroenolate Complexes
Arlow, Sophie I.
Hartwig, John F.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (45) : 16088 - 16091
[3] Mechanistic and Computational Studies of Oxidatively-Induced Aryl-CF3 Bond-Formation at Pd: Rational Design of Room Temperature Aryl Trifluoromethylation
Ball, Nicholas D.
Gary, J. Brannon
Ye, Yingda
Sanford, Melanie S.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (19) : 7577 - 7584
[4] Aryl-CF3 Bond-Forming Reductive Elimination from Palladium(IV)
Ball, Nicholas D.
Kampf, Jeff W.
Sanford, Melanie S.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (09) : 2878 - +
[5] Direct and Autocatalytic Reductive Elimination from Gold Complexes ([(Ph3P)Au(Ar)(CF3)(X)], X = F, Cl, Br, I): The Key Role of Halide Ligands
Bhattacharjee, Rameswar
Nijamudheen, A.
Datta, Ayan
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2017, 23 (17) : 4169 - 4179
[6] Synthesis of Au(I) Trifluoromethyl Complexes. Oxidation to Au(III) and Reductive Elimination of Halotrifluoromethanes
Blaya, Maria
Bautista, Delia
Gil-Rubio, Juan
Vicente, Jose
[J]. ORGANOMETALLICS, 2014, 33 (22) : 6358 - 6368
[7] Synthesis, Reactivity, and Catalytic Applications of Isolable (NHC)Cu(CHF2) Complexes
Bour, James R.
Kariofillis, Stavros K.
Sanford, Melanie S.
[J]. ORGANOMETALLICS, 2017, 36 (07) : 1220 - 1223
[8] Carbon-Carbon Bond-Forming Reductive Elimination from Isolated Nickel(III) Complexes
Bour, James R.
Camasso, Nicole M.
Meucci, Elizabeth A.
Kampf, Jeff W.
Canty, Allan J.
Sanford, Melanie S.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (49) : 16105 - 16111
[9] Oxidation of Ni(II) to Ni(IV) with Aryl Electrophiles Enables Ni-Mediated Aryl-CF3 Coupling
Bour, James R.
Camasso, Nicole M.
Sanford, Melanie S.
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (25) : 8034 - 8037
[10] Modern Carbon-Fluorine Bond Forming Reactions for Aryl Fluoride Synthesis
Campbell, Michael G.
Ritter, Tobias
[J]. CHEMICAL REVIEWS, 2015, 115 (02) : 612 - 633

← 1 2 3 4 5 6 7 →