- Photocatalytic Decarboxylative Coupling of Aliphatic N-hydroxyphthalimide Esters with Polyfluoroaryl Nucleophiles
-
Polyfluoroarenes are an important class of compounds in medical and material chemistry. The synthesis of alkylated polyfluoroarenes remains challenging. Here we describe a decarboxylative coupling reaction of N-hydroxyphthalimide esters of aliphatic carboxylic acids with polyfluoroaryl zinc reagents (Zn-ArF) via synergetic photoredox and copper catalysis. This method readily converts primary and secondary alkyl carboxylic acids into the corresponding polyfluoroaryl compounds, which could have a wide range of F-content (2F-5F) and variable F-substitution patterns on the aryl groups. Broad scope and good functional group compatibility were achieved, including on substrates derived from natural products and pharmaceuticals. Mechanistic study revealed that a [Cu-(ArF)2] species could be responsible for the transfer of polyfluoroaryl groups to the alkyl radicals.
- Hu, Xile,Lavrencic, Lara,Mao, Runze,Yi, Xiangli
-
supporting information
p. 23557 - 23563
(2021/09/30)
-
- Controllable double CF2-insertion into sp2 C-Cu bond using TMSCF3: A facile access to tetrafluoroethylene-bridged structures
-
A highly efficient method for controllable double CF2-insertion into pentafluorophenylcopper species using TMSCF3 as difluoromethylene source has been developed. The newly generated fluoroalkylcopper(i) species, C6F5CF2CF2Cu, shows good reactivity towards a myriad of structurally diverse aryl, heteroaryl and alkenyl iodides. This protocol is easy to handle, ready to scale up and applicable for the synthesis of relative complex molecules, thus providing a convenient method for facile access to tetrafluoroethylene-bridged structures.
- Xie, Qiqiang,Zhu, Ziyue,Li, Lingchun,Ni, Chuanfa,Hu, Jinbo
-
p. 276 - 280
(2019/12/30)
-
- COPPER-CATALYZED C-H BOND ARYLATION
-
The present invention is a one-step method for efficiently converting carbon-hydrogen bonds into carbon-carbon bonds using a combination of aryl halides, a substrate, and a copper salt as catalyst. This method allows faster introduction of complex molecular entities, a process that would otherwise require many more steps. This invention is particularly relevant for the organic synthesis of complex molecules such as, but not limited to, pharmacophores and explosives.
- -
-
Page/Page column 20
(2009/04/24)
-
- A comparative study of base-free arylcopper reagents for the transfer of aryl groups to boron halides
-
A comparative study on the reactivity and selectivity of arylcopper species in reactions with boron halides was performed. Mesitylcopper reacts with BX3 (X=Cl, Br) in toluene at low temperature under highly selective formation of the monosubstituted boranes MesBX2. The dimesitylboranes Mes2BX are gradually formed with a twofold excess of the organocopper reagent at elevated temperature. In contrast, pentafluorophenylcopper shows a tendency for formation of B(C6F5) 3 in reactions with BX3 irrespective of the stoichiometry used, suggesting a strong impact of electronic factors on the selectivity of the aryl transfer reaction. New procedures for the synthesis of the pentafluorophenylboron halides C6 F5BX2 (X=Cl: 57%; X=Br: 62%) and of tris(pentafluorophenyl)borane (80%) and related mixed-substituted triarylboranes from the base-free isolable pentafluorophenylcopper precursor have been developed.
- Sundararaman, Anand,J?kle, Frieder
-
p. 134 - 142
(2007/10/03)
-
- Photochemical reactions of [Re(η5-C5R5)(CO)3] (R = H or Me) with partially fluorinated benzenes: C-H and C-F activation
-
UV Irradiation of [Re(η5-C5R5)(CO)3] (R = Me or H) in the presence of C6F5H or 1,2,4,5-C6F4H2 effected intramolecular C-H activation, generating the hydrido complexes trans-[Re(η5-C5R5)(CO)2(Ar) FH] [(Ar)F = C6F5 or 2,3,5,6-C6F4H] as the principal photochemical products. The identities of the hydrido complexes were confirmed by independent thermal syntheses. The photoreaction of [Re(η5-C5Me5)(CO)3] with C6F5H also generated the fulvene complex [Re(η6-C5Me4CH2)(CO) 2(C6F5)] 2a and two bis(aryl) derivatives: cis-[Re(η5-C5Me5)(CO)2(C 6F5)2] 3a and [Re(η5-C5Me5)(CO)2(C 6F5)(2,3,5,6-C6F4H)] 4a in low yield. Complex 2a results from an intramolecular C-H activation, while 3a and 4a derive from a C-H and a C-F activation of a second molecule of pentafluorobenzene, respectively. The origin of the minor products was elucidated by showing that UV irradiation of [Re(η5-C5Me5)(CO)2-(C 6F5)H] in C6F5H produces 2a, 3a and 4a, while photolysis of 2a produces only 3a. The reaction of [Re(η5-C5Me5)-(CO)3] with 1,2,4,5-C6F4H2 gave analogues 2b and 4b as minor products. The photoreaction of [Re(η5-C5H5)(CO)3] in C6F5H or 1,2,4,5-C6F4H2 generated bis(aryl) compounds and the unusual binuclear complexes [Re2(η5-C5H5)(μ-η 1:η5-C5H4)(CO) 4(Ar)F] as the minor products. The binuclear complex with (Ar)F = 2,3,5,6-C6F4H has been characterized by X-ray crystallography. The Re-Re bond [3.0258(7) A] is close to collinear with the Re-C (aryl) bond. One {Re(CO)2} unit is twisted by about 73.0° with respect to the other.
- Godoy, Fernando,Higgitt, Catherine L.,Klahn, A. Hugo,Oelckers, Beatriz,Parsons, Simon,Perutz, Robin N.
-
p. 2039 - 2047
(2007/10/03)
-