ChemInform Abstract: New Efficient Palladium‐Catalyzed Perfluoroalkylation of Carbon‐Carbon Multiple Bonds with F‐Alkyl Iodides. An Expedient Route to F‐Alkylated Alkyl and Alkenyl Iodides.

Ishihara, Takashi; Kuroboshi, Manabu; Okada, Yoshiji

doi:10.1002/chin.198723102

Cited by 4 publications

(4 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…3b,4c It is consistent with iodoperfluoroalkylation achieved in many different ways: by heating, photolysis, using a free-radical initiator or transition-metal catalyst (e.g., Pd, Fe, Zn, Ni species). 22 The expected radical nature of the process was confirmed by trapping experiments with radical scavengers, such as 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and butylated hydroxytoluene (BHT). 11 The efficiency of the benchmark reaction of perfluorobutyl iodide with phenylacetylene was completely shut down in the presence of TEMPO (0.5−2 equiv) and diminished by the employment of BHT (0.5−2 equiv).…”

Section: Iiii Iodoperfluoroalkylationmentioning

confidence: 88%

Pd-Catalyzed Perfluoroalkylative Aryloxycarbonylation of Alkynes with Formates as CO Surrogates

Gatlik

Chaładaj

2021

ACS Catal.

View full text Add to dashboard Cite

The highly toxic, inflammable, and odorless nature of CO causes problematic handling on laboratory-scale experiments. Replacement of CO cylinders by CO surrogates is particularly attractive, especially in the case of multicomponent reactions leading to valuable fluorinated products. We report a Pd-catalyzed three-component protocol for the direct synthesis of perfluoroalkyl-substituted α,β-unsaturated esters from acetylenes and perfluoroalkyl iodides, applying formates as convenient CO sources. The tandem reaction proceeds under mild conditions with excellent regio-and stereoselectivities toward the E-isomer (>95:5, E:Z). Detailed mechanistic investigations revealed that the process proceeds through an off-cycle, base-induced decomposition of formate to CO and phenoxide, which are reassembled on the Pd-center into an aryloxycarbonyl moiety, which is ultimately installed on the alkene scaffold. To complete the mechanistic picture of the reaction, the experimental study was supported by DFT calculations.

show abstract

Section: Iiii Iodoperfluoroalkylationmentioning

confidence: 88%

Pd-Catalyzed Perfluoroalkylative Aryloxycarbonylation of Alkynes with Formates as CO Surrogates

Gatlik

Chaładaj

2021

ACS Catal.

View full text Add to dashboard Cite

show abstract

“…For the synthesis of the diiodohydroquinone ethers 7a – i with two identical branched chains (X = I, R 1 = R 2 = –CH 2 CH(C m H 2 m +1 ) 2 ), the branched alkyl bromides were obtained from diethyl malonate by a sequence of alkylation [ 90 ], dealkoxycarbonylation [ 91 ], reduction [ 92 ], and bromination [ 93 ], were etherified with 2,5-diiodohydroquinone ( Scheme S1 ) [ 94 ]. The diiodohydoquinone ether 7k , with two semiperfluorinated chains (X = I, R 1 = R 2 = –(CH 2 ) 4 C 6 F 13 ), was prepared in an analogous way using tridecafluorodecyl bromide ( Schemes S2 and S3 ) [ 92 , 93 , 95 ]. For the synthesis of the non-symmetric dibromohydroquinone ethers 7l, m (X = Br, R 1 = –C n H 2 n +1 , R 2 = –(CH 2 ) 4 C 6 F 13 ) 4-benzyloxy-2,5-dibromophenol was alkylated with the appropriate alkyl bromide first, the benzyloxy group was cleaved by catalytic hydrogenation and then the semiperfluorinated chain was attached by alkylation of the phenolic OH group with tridecafluorodecyl bromide ( Scheme S4 ).…”

Section: Methodsmentioning

confidence: 99%

Effects of Lateral and Terminal Chains of X-Shaped Bolapolyphiles with Oligo(phenylene ethynylene) Cores on Self-Assembly Behaviour. Part 1: Transition between Amphiphilic and Polyphilic Self-Assembly in the Bulk

Poppe

Ebert

et al. 2017

Polymers

View full text Add to dashboard Cite

Polyphilic self-assembly leads to compartmentalization of space and development of complex structures in soft matter on different length scales, reaching from the morphologies of block copolymers to the liquid crystalline (LC) phases of small molecules. Whereas block copolymers are known to form membranes and interact with phospholipid bilayers, liquid crystals have been less investigated in this respect. Here, series of bolapolyphilic X-shaped molecules were synthesized and investigated with respect to the effect of molecular structural parameters on the formation of LC phases (part 1), and on domain formation in phospholipid bilayer membranes (part 2). The investigated bolapolyphiles are based on a rod-like π-conjugated oligo(phenylene ethynylene) (OPE) core with two glycerol groups being either directly attached or separated by additional ethylene oxide (EO) units to both ends. The X-shape is provided by two lateral alkyl chains attached at opposite sides of the OPE core, being either linear, branched, or semiperfluorinated. In this report, the focus is on the transition from polyphilic (triphilic or tetraphilic) to binary amphiphilic self-assembly. Polyphilic self-assembly, i.e., segregation of all three or four incorporated units into separate nano-compartments, leads to the formation of hexagonal columnar LC phases, representing triangular honeycombs. A continuous transition from the well-defined triangular honeycomb structures to simple hexagonal columnar phases, dominated by the arrangement of polar columns on a hexagonal lattice in a mixed continuum formed by the lipophilic chains and the OPE rods, i.e., to amphiphilic self-assembly, was observed by reducing the length and volume of the lateral alkyl chains. A similar transition was found upon increasing the length of the EO units involved in the polar groups. If the lateral alkyl chains are enlarged or replaced by semiperfluorinated chains, then the segregation of lateral chains and rod-like cores is retained, even for enlarged polar groups, i.e., the transition from polyphilic to amphiphilic self-assembly is suppressed.

show abstract

“…4 ], and that radical scavengers retarded the reaction. 34 Qiu and Burton extended the scope of the reaction to the use of alkene,1,2-diols and they found that the same reaction can be performed by using by peroxides as radical initiators supporting a radical mechanism (Scheme 2). 35 R F I + CH 2 and phenyl ketones react with alkenes to give the corresponding α,α-difluoro-γ-iodoketones (Scheme 3).…”

Section: Radical Reactionsmentioning

confidence: 99%

Palladium-Mediated Organofluorine Chemistry

Albéniz¹,

Casares²

2014

Advances in Organometallic Chemistry

View full text Add to dashboard Cite

ChemInform Abstract: New Efficient Palladium‐Catalyzed Perfluoroalkylation of Carbon‐Carbon Multiple Bonds with F‐Alkyl Iodides. An Expedient Route to F‐Alkylated Alkyl and Alkenyl Iodides.

Abstract: 102ChemInform Abstract Reaction of the olefins (II) or the alkynes (IV) with the perfluoroalkyl iodides (I) in the presence of Pd(0) produces the adducts (III) and (V) respectively.

Cited by 4 publications

References 1 publication

Pd-Catalyzed Perfluoroalkylative Aryloxycarbonylation of Alkynes with Formates as CO Surrogates

Pd-Catalyzed Perfluoroalkylative Aryloxycarbonylation of Alkynes with Formates as CO Surrogates

Effects of Lateral and Terminal Chains of X-Shaped Bolapolyphiles with Oligo(phenylene ethynylene) Cores on Self-Assembly Behaviour. Part 1: Transition between Amphiphilic and Polyphilic Self-Assembly in the Bulk

Palladium-Mediated Organofluorine Chemistry

Contact Info

Product

Resources

About