Metalation of o-alkyl- and o,o′-dialkylsubstituted alkylthiobenzenes with n-butyllithium, in the presence and absence of TMEDA, has been investigated. The results showed that metalation at the thioalkyl carbon probably occurs by direct attack of the organolithium reagent, although a transmetalation reaction cannot be excluded in some cases. It has also been found that benzylic, thio-methylic, and ring metalation occurs in ether alone, whereas mainly thio-methylic or ring metalation occurs in the presence of TMEDA. 相似文献
The generation of a series of α-methoxymethoxy-substituted arylmethyllithiums was achieved by direct metalation of the corresponding arylmethyl methoxymethyl ethers. While the effect of substituents at the benzylic position is straightforward, substituents located on the aromatic ring promote the set up of a competition between lateral and aromatic metalation, strongly affected by the position and relative ortho directing properties of the new substituent. The proposed methodology allows a simple approach to the generation of a wide array of functionalized organolithium reagents. 相似文献
The metalation of methyl phenyl sulfone (I) and methyl naphthyl sulfone (II) was investigated under a variety of conditions. The product species were determined qualitatively and quantitatively after characterization with some electrophilic agents. After the primary metalation at the methyl position, species of various metalation degrees were prsent simultaneously, including the 1,1,1-trimetalated derivatives. With high LiR/sulfone ratios, in addition to the products of the primary metalation, compounds arising from metalation of the aromatic ring were formed as well as those from reduction, cleavage, etc. 相似文献
Metalation of 2(4′-Isoxazolyl)-Δ2-oxazolines takes place initially and selectively on the C-5′-alkyl group. Subsequent metalation also proceeds at this position. Selective deprotection of the oxazoline was accomplished without disturbing the isoxazole ring. 相似文献
We show that imidazolium salts do not always give normal or even aromatic carbenes on metalation, and the chemistry of these ligands can be much more complicated than previously thought. N,N'-disubstituted imidazolium salts of type [(2-py)(CH(2))(n)(C(3)H(3)N(2))R]BF(4) react with IrH(5)(PPh(3))(2) to give N,C-chelated products (n = 0, 1; 2-py = 2-pyridyl; C(3)H(3)N(2) = imidazolium; R = mesityl, n-butyl, i-propyl, methyl). Depending on the circumstances, three types of kinetic products can be formed: in one, the imidazole metalation site is the normal C2 as expected; in another, the metalation occurs at the abnormal C4 site; and in the third, C4 metalation is accompanied by hydrogenation of the imidazolium ring. The bonding mode is confirmed by structural studies, and spectroscopic criteria can also distinguish the cases. Initial hydrogen transfer can take place from the metal to the carbene to give the imidazolium ring hydrogenation product, as shown by isotope labeling; this hydrogen transfer proves reversible on reflux when the abnormal aromatic carbene is obtained as final product. Care may therefore be needed in the future in verifying the structure(s) formed in cases where a catalyst is generated in situ from imidazolium salt and metal precursor. 相似文献
Poly(2,6-dimethyl-1,4-phenylene ether) (I) was metalated with butyllithium in tetrahydrofuran and with the N,N,N′,N′-tetramethylethylenediamine complex of butyllithium in a variety of solvents. In these cases, metalation occurred at both the ring and side chain positions, the former being preferred initially. Subsequently, there was an isomerization in favor of the side chain. At 25°C, there is no significant amount of polymer scission or crosslinking during metalation, but some crosslinking occurs on derivatizing with dimethyl sulfate and trimethylchlorosilane for high extents of ring metalation. With sodium and potassium alkyls, only side-chain metalation was observed. The metalated polymer reacts as a typical organometallic, allowing polymer modification by a wide variety of reactions. 相似文献
The anionic graft polymerization of vinyl monomers onto carbon fiber initiated by metallized carbon fiber was investigated. The metalation of polycondensed aromatic rings of the carbon fiber surface was achieved by the treatment of carbon fiber with n-butyl-lithium (BuLi) in N, N, N′, N′ -tetramethylethylenediamine (TMEDA) or hexamethylphosphorous triamide (HMPT) at 0°C. The anionic polymerization of methyl methacrylate (MMA) and styrene (St) was initiated by the metallized carbon fiber, and these polymers were grafted onto the surface. The conversion and the percentage of grafting increased with increasing amount of BuLi used for the metalation of carbon fiber. When 0.20 g carbon fiber was treated with 0.3 mmol BuLi in TMEDA, the percentage of grafting of PMMA and PSt reached a maximum value (PMMA, 34.5%; PSt, 37.1 %). Furthermore, the metalation of aromatic rings of carbon fiber also proceeds by the treatment with BuLi in HMPT. On the contrary, no grafting was observed when carbon fiber was treated with BuLi in tetrahydrofuran (THF) or toluene. This may be due to the fact that metalation of carbon fiber does not proceed in THF or toluene. 相似文献
The umpolung of glycals with samarium diiodide offers a simple route to novel carbohydrate‐derived nucleophilic reagents in a single step using a readily available reductant. The corresponding allyl samarium reagent that arises from the hexose series reacts with ketones at the C3 position with high stereoselectivity; carbon–carbon bond formation takes place only anti to the substituent at the C4 position of the dihydropyran ring. For the sialic acid series, the completely regio‐ and stereoselective coupling process of the samarium reagent occurs at the anomeric carbon atom and provides a new approach to the α‐C‐glycosides of N‐acetyl neuraminic acid. 相似文献
4-(4,5-Dihydro-4,4-dimethyl-2-isoxazolyl)-3-phenyl-5-silylmethylisozazole and 3-phenyl-5-silylmethyl-4-isoxazole-t-carboxamide derivatives were synthesized in synthetically useful yields from the corresponding oxazolyl-isoxazole or t-carboxamide by metalation of the isoxazole systems at the C(5) alkyl group followed by electrophilic quenching with either t-butylchlorodiphenylsilane or t-butylchlorodimethylsilane. The silylisoxazole systems were metalated at the C(5) position, producing the corresponding α-silyl carbanion, which upon quenching with MeOD produced C(5) deuterium incorporation. The reaction of silyloxazolylisoxazoles with titanium tetrachloride caused the oxazoline ring to open forming chloro-substituted carboxamide. The X-ray structure of a silyloxazolylisoxazole was obtained and indicates an “s-trans” ring juncture with respect to the heterocyclic rings. 相似文献
The copper-promoted reaction of β-lactams with t-butyl perbenzoate results in benzoyloxylation of the azetidin-2-one ring at the C-4 position. There is no competing reaction at the C-3 position, but reaction at exocyclic carbon α to nitrogen competes with ring substitution. 相似文献
A general synthesis of highly substituted 2‐naphthols based on a new carbanionic reaction sequence is demonstrated. The reaction exploits the dual nature of lithium bases consisting of consecutive ring opening of readily available coumarins with either LiNEt2 or LiNiPr2 into Z‐cinnamamides, thus generating a directing group in situ and allowing, by conformational freedom, a lateral directed remote metalation for ring closure to give the aryl 2‐naphthols in good to excellent yields. These transformations can be combined to provide a more efficient one‐pot process. Mechanistic insight into the remote lateral metalation step, demonstrating the requirement of Z‐cinnamamide, is described. Application of this methodology to the synthesis of highly substituted 3,3′‐diaryl BINOL ligands is also reported. 相似文献
The syntheses of 1-phenylazonaphthalene ( 1a ) and its [3′-methyl- ( 1b ), 4′-methoxy- ( 1c ), 3′-methoxy- ( 1d )] derivatives are described. Cyclopalladation of these azo ligands with Pd(II) acetate or Na2PdCl4 leads to complexes with Pd(II) coordinated on the azo Nβ-atom and a Pd? C σ-bond at C(2) in the naphthalene moiety. The preference of Pd(II) for this type of metalation at C(2) over the palladation at the ortho positions of the phenyl ring or at the peri position of the naphthyl ring is believed to be largely due to steric effects and the different reactivities of the two arene moieties. Substitution of the acetato-bridge with bromide or iodide allows the syntheses of the corresponding bromo- and iodo-bridged complexes, and a chloro-bridged dimer complex can be converted to a monomeric ethylenediamino-Pd(II)-azo species with ethylenediamine. Cyclopalladation of sulfonated azo ligands leads to water-soluble Pd(II) complexes with a Pd-C σ-bond at C(2). 相似文献
Substitution of the hydrogen atoms of the cyclopentadienyl ring of (N, N-dimethylaminomethyl)cymantrene by deuterium changes the direction of orientation of metalation of this amine. 相似文献
New general methodology of value in aromatic chemistry based on ortho-metalation sites in o-, m-, and p-anisic acids (1-3) (Scheme 1) is described. The metalation can be selectively directed to either of the ortho positions by varying the base, metalation temperature, and exposure times. Metalation of o-anisic acid (1) with s-BuLi/TMEDA in THF at -78 degrees C occurs exclusively in the position adjacente to the carboxylate. On the other hand, a reversal of regioselectivity is observed with n-BuLi/t-BuOK. With LTMP at 0 degrees C, the two directors of m-anisic acid (2) function in concert to direct introduction of the metal between them while n-BuLi/t-BuOK removes preferentially the proton located ortho to the methoxy and para to the carboxylate (H-4). s-BuLi/TMEDA reacts with p-anisic acid (3) exclusively in the vicinity of the carboxylate. According to these methodologies, routes to very simple methoxybenzoic acids with a variety of functionalities that are not easily accessible by other means have been developed (Table 1). 相似文献
Simultaneous study of para nitrostilbenes by X-ray diffraction and 13C nuclear magnetic resonance shows a quantitative relationship between the effect of a para nitro substituent on the chemical shift of ethylenic carbon not adjacent to the substituted phenyl ring and the dihedral angle between this phenyl ring and the central double bond. The alternative introduction of substituents in each phenyl ring discloses at the position of carbon β a certain π-polarization which extends to the double bond and to an unsaturated group carried by carbon α. 相似文献
The para ‐selective C−H alkylation of aniline derivatives furnished with a pyrimidine auxiliary is herein reported. This reaction is proposed to take place via an N−H‐activated cyclometalate formed in situ. Experimental and DFT mechanistic studies elucidate a dual role of the ruthenium catalyst. Here the ruthenium catalyst can undergo cyclometalation by N−H metalation (as opposed to C−H metalation in meta ‐selective processes) and form a redox active ruthenium species, to enable site‐selective radical addition at the para position. 相似文献
An enzymatic solution to the problem of obtaining 13C/15N-labeled nucleotides that are deuterated uniquely at the H2' ' position within the ribose ring is presented. Selective deuteration occurs with an overall yield of >80%. The deuteron at the H2' ' position allows measurement of the scalar and residual dipolar couplings for the bond vectors attached to the C2' carbon of each ribose sugar. These data allow the accurate determination of sugar conformation. Interesting DNA double helices of 2-3 turns are now within the reach of solution NMR spectroscopy. As an example, these labeled nucleotides are incorporated uniquely at positions 6-14 in a 20-bp DNA sequence containing the adenovirus major late promoter. 相似文献
The direction of halogen addition to N-arylsulfonyl-1,4-benzoquinone monoimines dialkyl-substituted in the quinoid ring is governed by the steric factors: the size and position of the substituent, the halogen volume, and the position of the substituent at the nitrogen. The first stage of halogenation of N-arylsulfonyl-4-aminophenols with two alkyl substituents in the phenylsulfonyl ring largely occurs as electrophilic substitution. 相似文献
The metalation of the tetradentate molecule pyrphyrin by copper substrate atoms on a Cu(111) surface is studied. Pyrphyrin, in contrast to porphyrin, consists of four fused pyridine groups instead of pyrrol groups. Using thermal desorption spectroscopy (TDS ) and N 1s X‐ray photoelectron spectroscopy (XPS ), we show that metalation of the monolayer of pyrphyrin with Cu atoms from the Cu(111) surface occurs at 377 K. The formation of an extended two‐dimensional (2D) network is observed with scanning tunneling microscopy (STM ). A honeycomb‐like lattice of metalated pyrphyrin molecules is formed by intermolecular connection via the two cyano groups at the periphery of pyrphyrin as well as Cu adatoms. Dehydrogenation at the periphery of the molecule is observed during annealing at 520 K. The surface‐adsorbed metal‐pyrphyrin has the potential to serve as a molecular catalyst. 相似文献