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Ipso-arylation

The synthesis of the tellurophene-containing low-bandgap polymer PDPPTe2T by microwave-assisted, palladium-catalyzed, ipso-arylative polymerization of 2,5-bis[(a,a-diphenyl)methyl]tellurophene in the presence of diketopyrrolopyrrole (DPP) monomer was reported (14AG(1)10691). This is the first PV device prepared from a tellurophene polymer. IPCE measurements showed that substitution from sulfur to tellurium causes a red shift in absorption and enables donor materials to collect up to 1 pm. [Pg.144]

As described above regarding the behavior of aromatic carboxyhc acids, tert-benzyl alcohols are also unique substrates, which undergo not only hydroxy-directed ortho-arylation via C—H bond cleavage, but also ipso-arylation via C—C bond cleavage involving P-carbon elimination with the hberation of a ketone molecule (Scheme 4.84) [88]. [Pg.151]

The preparation of aromatic fluorine compounds may be accomplished by direct fluorination or by fluonnation of organometallic intermediates. Tlte ipso fluorination of an aryl organometallic derivative with a positive fluorine reagent allows control over the regioselectivity of the fluorination and offers advantages in the preparation of F-labeled materials [II, 50],... [Pg.148]

In contrast to 2,3-dioxygenases, the related ipso/ortho oxygenation of aryl carbox-ylates has received considerable less attention and has hardly been utilized by the synthetic community, so far. Biooxidation of benzoic acid and P-naphthalene carboxylate provide access to corresponding 1,2-dihydroxylated dihydroaryl compounds in excellent stereoselectivity (Scheme 9.35), analogous to TDO- and NDO-mediated ortho/meta oxygenations. Whole-cell-mediated biotransformations were performed with mutant strains of Rahtonia and Pseudomonas and enable access to preparative quantities in >5 gl titers [261,262]. [Pg.262]

An example of this displacement between a pyridine nitrogen atom and an aryl halide is shown in Scheme 21. When 2-pyridyl acetates 138 were C-acylated with 2-halobenzoyl chlorides, the enolized products 139 resulting from the reaction suffered an intramolecular nucleophilic attack of the pyridine nitrogen atom onto the ipso-position to give benzo[c]quinolizinium salts 140 as intermediates. Loss of HC1 gas from 140 afforded benzo[c]quinolizine derivatives 141 <2002JOC2082>. [Pg.24]

Incorporation of additional donor functionality into the periphery of phosphinomethanide ligands also has dramatic consequences for the structures of their alkali metal complexes. The complex [Li C(SiMe2Ph)(PMe2)2 ]3 (49) crystallizes as solvent-free cyclic tri-mers (Fig. 18), in which each lithium is primarily coordinated by two P atoms from one ligand and the carbanion center of an adjacent ligand (138, 139). This is supplemented by an essentially -interaction with the ipso and an ortho-carbon of the phenyl ring associated with the carbanion bonded to lithium. Each Li is thus bound by two P atoms, two aryl carbons, and a central carbon of the phosphinomethanide ligands. [Pg.80]

Recently, Curran described a procedure using triethylborane for the synthesis of spirooxindoles and spirodihydroquinolones through intramolecular addition of aryl radicals at the ipso position 4-alkoxy-substituted aromatic rings [15]. The key step for a formal synthesis of the vasopressin inhibitor SR121463A is described in Scheme 5. The initiation was performed with Et3B in an open to air reaction vessel. [Pg.85]

In these reaetions, the most reliable mechanism is considered to involve the initial metal-coordination at the nitrogen atom of the pyridine ring and the subsequent attack of an alkyl or aryl anion at the most probable cationic sites on the ring, namely, the 2- and/or 4-position of the ring. If a 2-halogen substituted pyridine is used, the nucleophilic anion attacks the 6-position. Thus, the addition is a more prefered reaction than the ipso-substitution as shown in reaction (29). The substitution of amide or phenyl-... [Pg.36]

Under the influence of a Lewis acid, Cjq can be arylated via a Eriedel-Crafts reaction (see Section 8.6). A similar reaction occurs with CggEjg where ipso substitution of fluorine atoms takes place [68]. The fluorofullerene is treated with FeClj in benzene for two weeks (Scheme 9.8). Electrophilic substitution leads to arylated C5QFjg Ph with n = 1-3. Probably due to steric reasons the 5-substitution is not observed in this arylation. [Pg.277]


See other pages where Ipso-arylation is mentioned: [Pg.101]    [Pg.295]    [Pg.3530]    [Pg.146]    [Pg.92]    [Pg.151]    [Pg.152]    [Pg.153]    [Pg.101]    [Pg.295]    [Pg.3530]    [Pg.146]    [Pg.92]    [Pg.151]    [Pg.152]    [Pg.153]    [Pg.820]    [Pg.16]    [Pg.702]    [Pg.143]    [Pg.702]    [Pg.376]    [Pg.6]    [Pg.224]    [Pg.52]    [Pg.198]    [Pg.199]    [Pg.284]    [Pg.777]    [Pg.1120]    [Pg.8]    [Pg.8]    [Pg.9]    [Pg.10]    [Pg.49]    [Pg.408]    [Pg.136]    [Pg.16]    [Pg.16]    [Pg.76]    [Pg.79]    [Pg.168]    [Pg.211]   
See also in sourсe #XX -- [ Pg.28 , Pg.151 ]




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Ipso attack aryl radicals

Silanes aryl, ipso substitution with electrophile

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