- Aryl or heteroaryl methoxylation reaction method
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The invention discloses an aryl or heteroaryl methoxylation reaction method. The method comprises the following steps: preparing a substrate. The coupling agent, ligand, solvent, catalyst and base are mixed homogeneously in an inert gas to give the aryl or heteroaryl methoxy compounds. Compared with a methoxylation reaction method in the prior art, the method has the advantages that the reaction system conditions are mild, the usage amount of the catalyst and the ligand is low to 5% of the amount of the substrate material, and the catalytic efficiency is improved. The method has better compatibility to different substrate expansion and discovery of aryl halides or heteroaryl halides with different functional groups. The yield of aryl or heteroaryl methoxy compounds prepared by the method disclosed by the invention is 36% - 89%.
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Paragraph 0155-0161
(2021/11/21)
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- Copper-Catalyzed Methoxylation of Aryl Bromides with 9-BBN-OMe
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A Cu-catalyzed cross-coupling reaction between aryl bromides and 9-BBN-OMe to provide aryl methyl ethers under mild conditions is reported. The oxalamide ligand BHMPO plays a key role in the transformation. Various functional groups on bromobenzenes are well tolerated, providing the desired anisole products in moderate to high yields.
- Li, Chen,Song, Zhi-Qiang,Wang, Dong-Hui,Wang, Jing-Ru
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supporting information
p. 8450 - 8454
(2021/11/17)
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- Introduction of Cyclopropyl and Cyclobutyl Ring on Alkyl Iodides through Cobalt-Catalyzed Cross-Coupling
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A cobalt-catalyzed cross-coupling between alkyl iodides and cyclopropyl, cyclobutyl, and alkenyl Grignard reagents is disclosed. The reaction allows the introduction of strained rings on a large panel of primary and secondary alkyl iodides. The catalytic system is simple and nonexpensive, and the reaction is general, chemoselective, and diastereoconvergent. The alkene resulting from the cross-coupling can be transformed to substituted cyclopropanes using a Simmons-Smith reaction. The formation of radical intermediates during the coupling is hypothesized.
- Andersen, Claire,Ferey, Vincent,Daumas, Marc,Bernardelli, Patrick,Guérinot, Amandine,Cossy, Janine
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p. 2285 - 2289
(2019/03/29)
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- Catalyst-Controlled Selective Functionalization of Unactivated C-H Bonds in the Presence of Electronically Activated C-H Bonds
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A new chiral dirhodium tetracarboxylate catalyst, Rh2(S-2-Cl-5-BrTPCP)4, has been developed for C-H functionalization reactions by means of donor/acceptor carbene intermediates. The dirhodium catalyst contains four (S)-1-(2-chloro-5-bromophenyl)-2,2-diphenylcyclopropane-1-carboxylate ligands, in which all four 2-chloro-5-bromophenyl groups are on the same face of the catalyst, leading to a structure, which is close to C4 symmetric. The catalyst induces highly site selective functionalization of remote, unactivated methylene C-H bonds even in the presence of electronically activated benzylic C-H bonds, which are typically favored using earlier established dirhodium catalysts, and the reactions proceed with high levels of diastereo- and enantioselectivity. This C-H functionalization method is applicable to a variety of aryl and heteroaryl derivatives. Furthermore, the potential of this methodology was illustrated by sequential C-H functionalization reactions to access the macrocyclic core of the cylindrocyclophane class of natural products.
- Liu, Wenbin,Ren, Zhi,Bosse, Aaron T.,Liao, Kuangbiao,Goldstein, Elizabeth L.,Bacsa, John,Musaev, Djamaladdin G.,Stoltz, Brian M.,Davies, Huw M. L.
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supporting information
p. 12247 - 12255
(2018/09/27)
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- Barbier–Negishi Coupling of Secondary Alkyl Bromides with Aryl and Alkenyl Triflates and Nonaflates
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A mild and practical Barbier–Negishi coupling of secondary alkyl bromides with aryl and alkenyl triflates and nonaflates has been developed. This challenging reaction was enabled by the use of a very bulky imidazole-based phosphine ligand, which resulted in good yields as well as good chemo- and site selectivities for a broad range of substrates at room temperature and under non-aqueous conditions. This reaction was extended to primary alkyl bromides by using an analogous pyrazole-based ligand.
- Zhang, Ke-Feng,Christoffel, Fadri,Baudoin, Olivier
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supporting information
p. 1982 - 1986
(2018/02/06)
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- Nickel-Catalyzed C-O Bond-Cleaving Alkylation of Esters: Direct Replacement of the Ester Moiety by Functionalized Alkyl Chains
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Two efficient protocols for the nickel-catalyzed aryl-alkyl cross-coupling reactions using esters as coupling components have been established. The methods enable the selective oxidative addition of nickel to acyl C-O and aryl C-O bonds and allow the aryl-alkyl cross-coupling via decarbonylative bond cleavage or through cleavage of a C-O bond with high efficiency and good functional group compatibility. The protocols allow the streamlined, unconventional utilization of widespread ester groups and their precursors, carboxylic acids and phenols, in synthetic organic chemistry.
- Liu, Xiangqian,Jia, Jiaqi,Rueping, Magnus
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p. 4491 - 4496
(2017/07/24)
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- P -Selective (sp2)-C-H functionalization for an acylation/alkylation reaction using organic photoredox catalysis
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p-Selective (sp2)-C-H functionalization of electron rich arenes has been achieved for acylation and alkylation reactions, respectively, with acyl/alkylselenides by organic photoredox catalysis involving an interesting mechanistic pathway.
- Pandey, Ganesh,Tiwari, Sandip Kumar,Singh, Bhawana,Vanka, Kumar,Jain, Shailja
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p. 12337 - 12340
(2017/11/20)
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- Terminal-Selective Functionalization of Alkyl Chains by Regioconvergent Cross-Coupling
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Hydrocarbons are still the most important precursors of functionalized organic molecules, which has stirred interest in the discovery of new C?H bond functionalization methods. We describe herein a new step-economical approach that enables C?C bonds to be constructed at the terminal position of linear alkanes. First, we show that secondary alkyl bromides can undergo in situ conversion into alkyl zinc bromides and regioconvergent Negishi coupling with aryl or alkenyl triflates. The use of a suitable phosphine ligand favoring Pd migration enabled the selective formation of the linear cross-coupling product. Subsequently, mixtures of secondary alkyl bromides were prepared from linear alkanes by standard bromination, and regioconvergent cross-coupling then provided access to the corresponding linear arylation product in only two steps.
- Dupuy, Stéphanie,Zhang, Ke-Feng,Goutierre, Anne-Sophie,Baudoin, Olivier
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supporting information
p. 14793 - 14797
(2016/11/23)
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- Nickel-Catalyzed Kumada Coupling of Benzyl Chlorides and Vinylogous Derivatives
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Conditions for the fast Ni-catalyzed Kumada-type cross-coupling of functionalized benzyl and allyl chlorides with alkylmagnesium reagents were discovered. The use of Ni(acac)2-TMEDA (acac = acetylacetonate, TMEDA = N,N,N′,N′-tetramethyl-1,2-ethylenediamine) allows the presence of reactive functional groups on the electrophile. On the other hand, the use of diallyl ether was shown to provide fast coupling at low temperature with a low catalyst loading. The reaction seems to follow a radical pathway.
- Soler-Yanes, Rita,Guisán-Ceinos, Manuel,Bu?uel, Elena,Cárdenas, Diego J.
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supporting information
p. 6625 - 6629
(2016/02/19)
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- Reactivity of mixed organozinc and mixed organocopper reagents: 6. Nickel-catalyzed coupling of methylarylzincs with primary alkyl halides; An atom-economic aryl-alkyl coupling
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A nickel-catalyzed process for the cross-coupling of mixed arylzincs and primary alkyl halides has been developed. The reaction of a methylarylzinc with a primary alkyl halide in THF in the presence of NiCl2/PPh 3 takes place with selective aryl transfer at room temperature in moderate yields. This protocol provides an atom-economic alternative to aryl-primary alkyl coupling using diarylzincs.
- Pekel, ?zgen ?mür,Erdik, Ender
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experimental part
p. 7087 - 7090
(2012/01/06)
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- Generation of magnesium carbenoids from 1-chloroalkyl phenyl sulfoxides with a Grignard reagent and applications to alkylation and olefin synthesis
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Treatment of 1-chloroalkyl phenyl sulfoxides with a Grignard reagent at low temperature gave magnesium carbenoids in quantitative yields. The generated magnesium carbenoids were found to be stable at lower than -60°C for long periods of time and are reactive with Grignard reagents to give alkylated products. The reaction of the generated magnesium carbenoids with various kinds of lithium α-sulfonyl carbanions gave olefins with carbon-carbon bond-formation in good to high yields. This method offers a good way for the preparation of olefins. The scope and limitations of the above-mentioned reactions are described.
- Satoh, Tsuyoshi,Kondo, Atsushi,Musashi, Jun
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p. 5453 - 5460
(2007/10/03)
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- Metal cation-exchanged montmorillonite (Mn+-mont)-catalysed aromatic alkylation with aldehydes and ketones
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The alkylation of aromatic compounds with aldehydes and ketones in the presence of a variety of metal cation-exchanged montmorillonites (Mn+-mont; Mn+ = Zr4+, Al3+, Fe3+, Zn2+, H+, Na+) has been investigated. Al3+- and Zr4+-Monts are revealed to be effective as catalysts, while no reaction takes place with Na+-mont. Al3+-Mont-catalysed alkylation of phenol with several aldehydes produces mainly or almost solely the corresponding gem-bis(hydroxyphenyl)alkanes (bisphenols) in good yields, while that with several ketones affords selectively the corresponding alkylphenols in moderate to good yields. The alkylation always occurs at the carbonyl carbon without any skeletal rearrangement and the kind of products depends much on the steric hindrance of an electrophilic intermediary carbocation. The alkylation of anisole, veratrole and p-cresol proceeds well, while that of toluene, benzene, chlorobenzene and nitrobenzene scarcely occurs.
- Tateiwa, Jun-Ichi,Hayama, Ei,Nishimura, Takahiro,Uemura, Sakae
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p. 1923 - 1928
(2007/10/03)
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- Alkylation of Aldehyde (Arenesulfonyl)hydrazones with Trialkylboranes
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(Arenesulfonyl)hydrazone derivatives of aryl aldehydes are readily alkylated by trialkylboranes in the presence of base to generate new organoboranes that may be converted to the corresponding substituted alkanes or alcohols depending upon the reaction conditions chosen. Both tosyl- and trisylhydrazone derivatives can be utilized in the reaction, which tolerates a variety of functional groups, making it a versatile alternative to both the Grignard and Suzuki-coupling reactions.
- Kabalka, George W.,Maddox, John T.,Bogas, Ekaterini,Kelley, Shane W.
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p. 3688 - 3695
(2007/10/03)
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- A Facile Alkylation of Aryl Aldehyde Tosylhydrazone with Trialkylboranes
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Trialkylboranes readily alkylate aryl aldehyde tosylhydrazones to produce either the corresponding arylalkane or aryl alcohol in excellent yields.
- Kabalka, George W.,Maddox, John T.,Bogas, Ekaterini
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p. 5530 - 5531
(2007/10/02)
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- Reduction of Monobenzylic Alcohols with Sodium Borohydride/Trifluoroacetic Acid
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Sodium borohydride/trifluoroacetic acid readily effects the reduction of monobenzylic alcohols to afford the corresponding hydrocarbons in moderate to high yields.
- Nutaitis, Charles F.,Bernardo, Joseph E.
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p. 487 - 493
(2007/10/02)
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- REDUCTIVE TRANSFORMATIONS WITH TRIMETHYLSILYL CHLORIDE-SODIUM IODIDE. A NEW SYNTHESIS OF 4H-1,3-OXAZINES
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1-Arylalkenes and 1-arylalkanols are reduced to arylalkanes on heating with trimethylsilyl chloride/sodium iodide in CH3CN.Under similar conditions enones, dialkylated in the β-position of the double bond, give 4H-1,3-oxazines.
- Ghera, Eugene,Maurya, Rakesh,Hassner, Alfred
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p. 4741 - 4744
(2007/10/02)
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- CONVENIENT METHOD OF OBTAINING 2-CYANO-4-ALKYLPHENOLS, 4-CYANOPHENOL AND 4-CYANOANILINE.
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A convenient method is described of obtaining 2-cyano-4-alkylphenols and 4-cyanophenol by substituting brombine atom for the cyano group in the respective bromoanisoles and demethylation of the cyanoalkylanisoles. It is suggested to prepare 4-cyanoaniline by reduction of 4-cyano-nitrobenzene with aqueous hydrazine solutions.
- Adamska,Dabrowski,Dziabuszek
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