- Air-Stable Iron-Based Precatalysts for Suzuki-Miyaura Cross-Coupling Reactions between Alkyl Halides and Aryl Boronic Esters
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The development of an air-stable iron(III)-based precatalyst for the Suzuki-Miyaura cross-coupling reaction of alkyl halides and unactivated aryl boronic esters is reported. Despite benefits to cost and toxicity, the proclivity of iron(II)-based complexes to undergo deactivationviaoxidation or hydrolysis is a limiting factor for their widespread use in cross-coupling reactions compared to palladium-based or nickel-based complexes. The new octahedral iron(III) complex demonstrates long-term stability on the benchtop as assessed by a combination of1H NMR spectroscopy, M?ssbauer spectroscopy, and its sustained catalytic activity after exposure to air. The improved stability of the iron-based catalyst facilitates an improved protocol in which Suzuki-Miyaura cross-coupling reactions of valuable substrates can be assembled without the use of a glovebox and access a diverse scope of products similar to reactions assembled in the glovebox with iron(II)-based catalysts.
- Wong, Alexander S.,Zhang, Bufan,Li, Bo,Neidig, Michael L.,Byers, Jeffery A.
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p. 2461 - 2472
(2021/11/01)
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- Flow Friedel–Crafts alkylation of 1-adamantanol with arenes using HO-SAS as an immobilized acid catalyst
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In this communication flow Friedel–Crafts alkylation was studied using hydroxy-substituted sulfonic acid-functionalized silica as a catalyst and 1-adamantanol as a model substrate. The reaction of 1-adamantanol (1a) with toluene (2a) proceeded well with 5 min of residence time at 120°C to give good yield of 1-tolyladamantane (3a) as a 1:9 mixture of meta and para isomers. When the flow synthesis was carried out over 2.5 hr of running time, the collected five fractions contain the product 3a in 97–92% yields, suggesting the durability of the catalyst.
- Kasakado, Takayoshi,Hyodo, Mamoru,Furuta, Akihiro,Kamardine, Aina,Ryu, Ilhyong,Fukuyama, Takahide
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p. 2253 - 2257
(2020/12/15)
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- Rational Design of an Iron-Based Catalyst for Suzuki–Miyaura Cross-Couplings Involving Heteroaromatic Boronic Esters and Tertiary Alkyl Electrophiles
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Suzuki–Miyaura cross-coupling reactions between a variety of alkyl halides and unactivated aryl boronic esters using a rationally designed iron-based catalyst supported by β-diketiminate ligands are described. High catalyst activity resulted in a broad substrate scope that included tertiary alkyl halides and heteroaromatic boronic esters. Mechanistic experiments revealed that the iron-based catalyst benefited from the propensity for β-diketiminate ligands to support low-coordinate and highly reducing iron amide intermediates, which are very efficient for effecting the transmetalation step required for the Suzuki–Miyaura cross-coupling reaction.
- Byers, Jeffery A.,Crockett, Michael P.,Li, Bo,Wong, Alexander S.
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supporting information
p. 5392 - 5397
(2020/03/04)
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- Resolution of Vaulted Biaryl Ligands via Borate Esters of Quinine and Quinidine
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Given the sudden and unexplained rise in the cost of (+)- A nd (-)-sparteine, an alternative method for the resolution of vaulted biaryls has been developed. This method involves the reaction of a racemic vaulted biaryl ligand with one equivalent of BH3·SMe2 and one equivalent of either quinine or quinidine. A precipitate then forms from the resulting mixture of diastereomeric borates as a result of differential solubilities. Hydrolysis of the precipitate then liberates the (S)-ligand in the case of quinine and the (R)-ligand in the case of quinidine, both with >99% ee. This method has been applied to 16 different vaulted biaryl ligands, including 10 whose preparation is described here for the first time. In addition, proof of principle has been demonstrated for the dynamic thermodynamic resolution of the vaulted biaryl ligands with this method in combination with a nonchiral copper(II) complex that can racemize the ligand.
- Cagnon, Brian R.,Mohammadlou, Aliakbar,Wulff, William D.,Yin, Xiaopeng,Zheng, Li
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p. 10432 - 10450
(2020/09/23)
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- Preparation method of 1-phenyl adamantane and obtained 1-phenyl adamantane
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The invention relates to a preparation method of 1-phenyl adamantane and the obtained 1-phenyl adamantane, and belongs to the technical field of drug synthesis. The preparation method comprises the following steps: taking 1-bromoadamantane and bromobenzen
- -
-
Paragraph 0042-0060; 0062-0065
(2020/08/02)
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- Adamantane-containing compound, high polymer, mixture, composition, and electronic device
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The invention discloses an adamantane-containing compound represented by general formula (1), and a high polymer, a mixture, a composition and an electronic device containing the same. Adamantane andan electron-deficient unit are connected to serve as a core unit, and then are matched with other functional units in order to effectively increase the intermolecular distance and reduce the intermolecular interaction, so the effects of reducing exciton quenching and improving the energy utilization rate are achieved, and the performances of the compound and the related device are further improved.
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Paragraph 0236-0239; 0267-0270
(2020/02/20)
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- Iron-Catalyzed Suzuki-Miyaura Cross-Coupling Reactions between Alkyl Halides and Unactivated Arylboronic Esters
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An iron-catalyzed cross-coupling reaction between alkyl halides and arylboronic esters was developed that does not involve activation of the boronic ester with alkyllithium reagents nor requires magnesium additives. A combination of experimental and theoretical investigations revealed that lithium amide bases coupled with iron complexes containing deprotonated cyanobis(oxazoline) ligands were best to obtain high yields (up to 89%) in catalytic cross-coupling reactions. Mechanistic investigations implicate carbon-centered radical intermediates and highlight the critical importance of avoiding conditions that lead to iron aggregates. The new iron-catalyzed Suzuki-Miyaura reaction was applied toward the shortest reported synthesis of the pharmaceutical Cinacalcet.
- Crockett, Michael P.,Tyrol, Chet C.,Wong, Alexander S.,Li, Bo,Byers, Jeffery A.
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supporting information
p. 5233 - 5237
(2018/09/12)
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- Ni-Catalyzed Electrochemical Decarboxylative C-C Couplings in Batch and Continuous Flow
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An electrochemically driven, nickel-catalyzed reductive coupling of N-hydroxyphthalimide esters with aryl halides is reported. The reaction proceeds under mild conditions in a divided electrochemical cell and employs a tertiary amine as the reductant. This decarboxylative C(sp3)-C(sp2) bond-forming transformation exhibits excellent substrate generality and functional group compatibility. An operationally simple continuous-flow version of this transformation using a commercial electrochemical flow reactor represents a robust and scalable synthesis of value added coupling process.
- Li, Hui,Breen, Christopher P.,Seo, Hyowon,Jamison, Timothy F.,Fang, Yuan-Qing,Bio, Matthew M.
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supporting information
p. 1338 - 1341
(2018/03/09)
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- Initiation in Photoredox C-H Functionalization Reactions. Is Dimsyl Anion a Key Ingredient?
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Previous studies have reported the arylation of unactivated arenes with ArX, base (KOtBu or NaOtBu), and an organic additive at high temperatures. Recently, we showed that this reaction proceeds in the absence of additives at rt but employs UV-vis light. However, details of mechanisms that can use a photoinduced base-promoted homolytic aromatic substitution reaction (photo-BHAS) have remained elusive until now. This work examines different mechanistic routes of the essential electron-transfer step (ET) of this reaction in order to identify a possible path for the formation of 1-adamantyl radicals from 1-haloadamantanes (initiation step). On the basis of photochemical and photophysical experiments and computational studies, we propose an unprecedented initiation step that could also be applied to other ET reactions performed in DMSO. For the first time, it is reported that dimsyl anion, formed from a strong base and DMSO (solvent), is responsible for inducing the initiation by a photo-BHAS process on alkyl halides.
- Budén, María E.,Bardagí, Javier I.,Puiatti, Marcelo,Rossi, Roberto A.
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supporting information
p. 8325 - 8333
(2017/08/23)
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- Alkyl?(Hetero)Aryl Bond Formation via Decarboxylative Cross-Coupling: A Systematic Analysis
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Suzuki, Negishi, and Kumada couplings are some of the most important reactions for the formation of skeletal C?C linkages. Their widespread use to forge bonds between two aromatic rings has enabled every branch of chemical science. The analogous union between alkyl halides and metallated aryl systems has not been as widely employed due to the lack of commercially available halide building blocks. Redox-active esters have recently emerged as useful surrogates for alkyl halides in cross-coupling chemistry. Such esters are easily accessible through reactions between ubiquitous carboxylic acids and coupling agents widely used in amide bond formation. This article features an amalgamation of in-house experience bolstered by approximately 200 systematically designed experiments to accelerate the selection of ideal reaction conditions and activating agents for the cross-coupling of primary, secondary, and tertiary alkyl carboxylic acids with both aryl and heteroaryl organometallic species.
- Sandfort, Frederik,O'Neill, Matthew J.,Cornella, Josep,Wimmer, Laurin,Baran, Phil S.
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supporting information
p. 3319 - 3323
(2017/03/17)
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- Copper-catalyzed cross-coupling reactions of non-activated primary, secondary or tertiary alkyl chlorides with phenylmagnesium bromide
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Efficient copper-catalyzed cross-coupling reactions of non-activated alkyl chlorides, including primary, secondary, and tertiary alkyl chlorides, with phenyl Grignard reagents were achieved. Preparation of phenylmagnesium bromide in 2-methyltetrahydrofuran is critical for the success of the reaction. This protocol expands the synthetic toolbox for the construction of C[sbnd]C bonds of non-activated primary, secondary, and tertiary alkyl chlorides via copper-catalyzed cross-coupling.
- Tao, Chuanzhou,Sun, Lei,Wang, Bin,Liu, Zhou,Zhai, Yadong,Zhang, Xiulian,Shi, Dahua,Liu, Weiwei
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supporting information
p. 305 - 308
(2017/01/03)
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- A pyridinium modified β-cyclodextrin: An ionic supramolecular ligand for palladium acetate in C-C coupling reactions in water
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An ionic Pd(ii) complex stabilized by a water soluble pyridinium modified β-cyclodextrin was prepared and characterized by NMR, mass spectrometry, FT-IR spectroscopy, UV-visible spectroscopy and DLS (dynamic light scattering). The resulting Pd(ii)@Pyr:β-CD complex showed very good catalytic activity in Suzuki-Miyaura and Heck C-C coupling reactions in an environmentally benign water medium. Good to excellent yields were obtained for the coupling of various aryl halides including chlorides with phenylboronic acid/styrene using a catalytic amount of Pd(ii)@Pyr:β-CD. This homogeneous catalyst can be reused and recycled more than six times with only marginal loss of its catalytic activity.
- Khan, Raihana Imran,Pitchumani, Kasi
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p. 5518 - 5528
(2016/10/21)
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- Redox-Active Esters in Fe-Catalyzed C-C Coupling
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Cross-couplings of alkyl halides and organometallic species based on single electron transfer using Ni and Fe catalyst systems have been studied extensively, and separately, for decades. Here we demonstrate the first couplings of redox-active esters (both isolated and derived in situ from carboxylic acids) with organozinc and organomagnesium species using an Fe-based catalyst system originally developed for alkyl halides. This work is placed in context by showing a direct comparison with a Ni catalyst for >40 examples spanning a range of primary, secondary, and tertiary substrates. This new C-C coupling is scalable and sustainable, and it exhibits a number of clear advantages in several cases over its Ni-based counterpart.
- Toriyama, Fumihiko,Cornella, Josep,Wimmer, Laurin,Chen, Tie-Gen,Dixon, Darryl D.,Creech, Gardner,Baran, Phil S.
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supporting information
p. 11132 - 11135
(2016/10/12)
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- Alkylation of aromatic compounds with 1-bromoadamantane in the presence of metal complex catalysts
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Synthesis of aryladamantanes was performed by reaction of 1-bromoadamantane with aromatic compounds in the presence of metal complex catalysts containing Mo, Cr, W, Cu, and Co.
- Khusnutdinov,Shchadneva,Khisamova
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p. 1545 - 1550
(2015/12/30)
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- Direct C(sp2)-C(sp3) cross-coupling of diaryl zinc reagents with benzylic, primary, secondary, and tertiary alkyl halides
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The direct C(sp2)-C(sp3) cross-coupling of diaryl zinc reagents with benzylic, primary, secondary, and tertiary alkyl halides proceeded in the absence of coordinating ethereal solvents at ambient temperature without the addition of a catalyst. The C(sp2)-C(sp3) cross-coupling showed excellent functional-group tolerance, and products were isolated in high yields, generally without the requirement for purification by chromatography. This process represents an expedient, operationally simple method for the construction of new C(sp2)-C(sp3) bonds. Zinc and you'll miss it. Direct C(sp2)-C(sp3) cross-coupling of diaryl zinc reagents with alkyl halides proceeded rapidly at ambient temperature without a coordinating ethereal solvent or an added catalyst (see scheme). This versatile, operationally simple approach to C(sp2)-C(sp3) bond formation enables the expedient construction of a diverse array of carbon-based structural motifs.
- Dunsford, Jay J.,Clark, Ewan R.,Ingleson, Michael J.
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supporting information
p. 5688 - 5692
(2015/05/19)
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- Synthesis and ring-opening reaction of novel 1,3-dehydroadamantanes possessing phenyl and alkoxyl substituents
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A series of novel 1,3-dehydroadamantanes (DHAs) possessing phenyl or alkoxyl substituents, such as 5-phenyl-1,3-dehydroadamantane, 5-butyl-7-phenyl-1,3-dehydroadamantane, 5-methoxy-1,3-dehydroadamantane, 5-butoxy-1,3-dehydroadamantane, 5-butyl-7-methoxy-1,3-dehydroadamantane, and 5-butoxy-7-butyl-1,3-dehydroadamantane were synthesized and subjected to react with acidic compounds. 1,3-Dibromoadamantanes carrying phenyl or alkoxyl substituents were converted into the corresponding DHAs via the intramolecular Wurtz-type coupling reactions with lithium metal in THF in 23-62% yields. Ring-opening reactions of DHAs readily occurred with acetic acid or methanol under acidic conditions to form various 1-acetoxyadamantanes or 1-methoxyadamantanes containing phenyl or alkoxyl groups. The resulting 1-butyl-3-methoxy-5-phenyladamantane, 1-acetoxy-3-butyl-5-phenyladamantane, 1-acetoxy-3-butyl-5-methoxyadamantane, 1-acetoxy-3-butoxy-5-butyladamantane, and 1-butoxy-3-butyl-5-methoxyadamantane possessed stereogenic center. The high reactivity of the inverted 1,3-carbon-carbon σ-bond in DHAs toward the acidic compounds indicated the high electron density, which was supported by the sp2 character of cyclopropane rings in DHAs estimated by J C-H coupling constants in the 13C NMR analyzes.
- Inomata, Sotaro,Harada, Yusuke,Matsuoka, Shin-Ichi,Ishizone, Takashi
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p. 3238 - 3248
(2013/04/24)
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- Nickel-catalyzed carbon-carbon bond-forming reactions of unactivated tertiary alkyl halides: Suzuki arylations
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The first Suzuki cross-couplings of unactivated tertiary alkyl electrophiles are described. The method employs a readily accessible catalyst (NiBr2·diglyme/4,4′-di-tert-butyl-2,2′-bipyridine, both commercially available) and represents the initial example of the use of a group 10 catalyst to cross-couple unactivated tertiary electrophiles to form C-C bonds. This approach to the synthesis of all-carbon quaternary carbon centers does not suffer from isomerization of the alkyl group, in contrast with the umpolung strategy for this bond construction (cross-coupling of a tertiary alkylmetal with an aryl electrophile). Preliminary mechanistic studies are consistent with the generation of a radical intermediate along the reaction pathway.
- Zultanski, Susan L.,Fu, Gregory C.
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supporting information
p. 624 - 627
(2013/03/14)
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- Kumadatamaocorriu coupling of alkyl halides catalyzed by an ironbisphosphine complex
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An iron(II) chloride complex possessing a sterically demanding ortho-phenylene-tethered bisphosphine ligand shows a high catalytic activity in the KumadaTamaoCorriu coupling of nonactivated alkyl halides with aryl Grignard reagents. Primary, secondary, and tertiary alkyl halides can participate as an electrophilic coupling partner. A radical clock experiment using (iodomethyl)cyclopropane exclusively gives the corresponding ring-opening coupling product, suggesting intermediacy of alkyl radical species.
- Hatakeyama, Takuji,Fujiwara, Yu-Ichi,Okada, Yoshihiro,Itoh, Takuma,Hashimoto, Toru,Kawamura, Shintaro,Ogata, Kazuki,Takaya, Hikaru,Nakamura, Masaharu
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supporting information; experimental part
p. 1030 - 1032
(2011/12/05)
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- A catalytic C-C bond-forming reaction between aliphatic fluorohydrocarbons and arylsilanes
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C-C coupling reactions between arylsilanes and alkylfluorides are efficiently catalyzed by disilyl cation 1. Primary as well as secondary alkylfluorides were quantitatively coupled with arylsilanes; however, in the case of tertiary fluorides, the hydrodef
- Luehmann, Nicole,Panisch, Robin,Mueller, Thomas
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experimental part
p. 533 - 537
(2010/10/19)
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- C-F bond-cleavage reactions of fluoroalkanes with magnesium reagents and without metal catalysts
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An unexpected C-F bond-cleavage reaction of unactlvated fluoroalkanes with the well-known Grlgnard reagents without using metal catalysts has been discovered. For example, a reaction between 1-fluorooctane and phenyl magnesium chloride gave n-octylbenzene In moderate yield. This coupling reaction via the activation of an unactlvated alkyl carbon-fluorine bond proceeds with phenylmagneslum chloride, whereas methylmagneslum chloride did not give the C-C cross-coupling product but rather a halogen exchange product.
- Matsubara, Kouki,Ishibashi, Tomoka,Koga, Yuji
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supporting information; experimental part
p. 1765 - 1768
(2009/09/06)
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- Silver-catalyzed cross-coupling reactions of alkyl bromides with alkyl or aryl Grignard reagents
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Treatment of secondary or tertiary alkyl bromides with alkyl Grignard reagents in the presence of catalytic amounts of silver bromide and potassium fluoride in CH2Cl2 afforded the corresponding cross-coupling products in reasonable yields. Moreover, silver showed catalytic activity for the cross-coupling reactions of alkyl bromides with aryl Grignard reagents.
- Someya, Hidenori,Yorimitsu, Hideki,Oshima, Koichiro
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supporting information; experimental part
p. 3270 - 3272
(2009/08/09)
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- PHOTOSENSITIVE COMPOSITION, COMPOUND FOR USE IN THE PHOTOSENSITIVE COMPOSITION AND PATTERN FORMING METHOD USING THE PHOTOSENSITIVE COMPOSITION
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The invention is related to an arylsulfonium salt compound having a polycyclic hydrocarbon structure in a cation moiety.
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- Photochromism of diarylethene single molecules in polymer matrices
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Robust fluorescent photoswitching molecules, having perylene bisimide as the fluorescent unit and diarylethene as the switching unit, were prepared, and their photochromic reactions were measured at the single-molecule level in various polymer matrices. T
- Fukaminato, Tuyoshi,Umemoto, Tohru,Iwata, Yasuhide,Yokojima, Satoshi,Yoneyama, Mitsuru,Nakamura, Shinichiro,Irie, Masahiro
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p. 5932 - 5938
(2008/02/04)
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- Alkylation of adamantane with alkyl halides catalyzed by ruthenium complexes
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The feasibility of catalytic alkylation of adamantane and 1-bromoadamantane with alkyl halides in the presence of ruthenium-containing catalysts was revealed. The optimum molar ratios between the catalyst components and the reactants, as well as the reaction conditions for the selective synthesis of mono-and dialkylsubstituted adamantane derivatives with a 70-98% yield, were determined. Nauka/Interperiodica 2006.
- Khusnutdinov,Schchadneva,Malikov,Dzhemilev
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p. 159 - 163
(2007/10/03)
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- The role of enthalpic and entropic factors in the isomerization equilibrium of aryladamantanes
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The chemical equilibrium of five positional isomerization reactions of aryladamantanes with different structures was studied in the liquid phase in the presence of AlCl3 in the range 303-423 K. Contributions to the equilibrium constants were analyzed using experimental and calculated data. The contributions were from symmetry, intermolecular interactions, differences in heat capacities of isomers, overall rotation of molecules, free or hindered rotation of groups in molecules, contribution of vibrations, differences in conformational composition, and intramolecular effects of interaction of substituents in molecules involved in the reaction. The significance of these contributions to the equilibrium constants of the transformations in question was shown. The enthalpies and changes in entropy for the reactions in the liquid and gaseous states were determined and discussed. A comparative analysis of the thermodynamic characteristics of positional isomerization of aryladamantanes, methyladamantanes, methyldiamantanes, and phenylcyclohexanes is given.
- Pimerzin,Sarkisova
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- Photochemical alkylation of ketene dithioacetal S,S-dioxides. An example of captodative olefin functionalization
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Radical alkylation of some ketene dithioacetal S,S-dioxides failed through the tin hydride promoted chain process but was successfully performed through stoichiometric photochemical initiation, either by electron transfer or hydrogen abstraction. In the first case, alkyl radicals were produced from tetralkylstannanes (t-Bu-, i-Pr-, n-Bu-SnR3) via radical cation fragmentation, while in the second case these were produced from alkanes (cyclohexane, adamantane) by benzophenone triplet. When bulky radicals (t-Bu, adamantyl) were involved, the addition occurred with complete diastereoselectivity.
- Gonzalez-Cameno, Ana Maria,Mella, Mariella,Fagnoni, Maurizio,Albini, Angelo
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p. 297 - 303
(2007/10/03)
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- Hafnium(IV)Trifluoromethanesulfonate, An Efficient Catalyst for the Friedel-Crafts Acylation and Alkylation Reactions
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Hafnium(IV) trifluoromethanesulfonate (hafnium(IV) triflate, Hf(OTf)4) was synthesized from hafnium tetrachloride and trifluoromethanesulfonic acid.The triflate thus prepared was found to be effective in the catalytic Friedel-Crafts acylation reactions of various substituted benzenes with acid anhydrides in lithium perchlorate-nitromethane (LiClO4-MeNO2).Lithium perchlorate-nitromethane is an excellent solvent system, and the catalytic activity of the Lewis acid was much improved in this medium.The product was obtained in up to 250000percent molar amounts baaed on the catalyst.Hafnium(IV) triflate was also found to be quite effective in the catalytic Friedel-Crafts alkylation reactions of aromatic compounds with alkyl chlorides.The reactions proceeded smoothly in the presence of 5percent molar amount of Hf(OTf)4 and 50percent molar amount of LiClO4 by using a slow addition procedure.
- Hachiya, Iwao,Moriwaki, Mitsuhiro,Kobayashi, Shu
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p. 2053 - 2060
(2007/10/02)
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- Adamantane derivatives in the prevention and treatment of cerebral ischemia
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A method for the prevention and treatment of cerebral ischemia using an adamantane derivative of the formula STR1 wherein R1 and R2 are identical or different, representing hydrogen or a straight or branched alkyl group of 1 to 6 C atoms or, in conjunction with N, a heterocyclic group with 5 or 6 ring C atoms; wherein R3 and R4 are identical or different, being selected from hydrogen, a straight or branched alkyl group of 1 to 6 C atoms, a cycloalkyl group with 5 or 6 C atoms, and phenyl; wherein R5 is hydrogen or a straight or branched C1 -C6 alkyl group, or a pharmaceutically-acceptable salt thereof, is disclosed.
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- SYNTHESIS AND STRUCTURE OF AROMATIC COMPOUNDS CARRYING TWO 1-ADAMANTYLS ON ADJACENT POSITIONS: 3,4-DI-1-ADAMANTYLTHIOPHENE, o-DI-1-ADAMANTYLBENZENE, AND 4,5-DI-1-ADAMANTYLPYRIDAZINE
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3,4-Di-1-adamantylthiophene, o-di-1-adamantylbenzene, and 4,5-di-1-adamantylpyridazine, which carry two bulky 1-adamantyl groups on adjacent positions, were satisfactorily synthesized starting from 1,5-di-1-adamantyl-3-thiapentane-1,5-dione.Synthesis, pro
- Nakayama, Juzo,Hasemi, Ryuji,Iwasaki, Fujiko
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p. 243 - 246
(2007/10/02)
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- Boron Tris(triflate) Catalyzed Adamantylation of Benzene and Toluene with 1- and 2-Haloadamantanes and Adamantanoyl Chlorides. Isomerization of Phenyl- and Tolyladamantanes
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Boron tris(triflate) catalyzed adamantylation of benzene and toluene was studied with isomeric 1- and 2-haloadamantanes.The alkylations give 1- and 2-phenyl- and isomeric tolyladamantanes in varying ratios.Interconversion of isomeric 2-phenyl(tolyl)adamantanes into the corresponding 1-phenyl(tolyl)adamantanes was observed through intermolecular isomerization involving adamantyl cations and adamantane, which is formed in significant amount in all the reactions.Decarbonylative alkylation of aromatics with adamantanoyl chlorides was also investigated.Adamantanoylated aromatics were formed only in very low amounts, the major product being adamantylated aromatics in accord with extensive decarbonylation of the adamantanoyl cations.The mechanism of the studies adamantylations was further substantiated by studying the boron tris(triflate) catalyzed isomerization of 1- and 2-aryladamantanes under comparable conditions.
- Olah, George A.,Farooq, Omar,Farnia, S. Morteza F.,Wu, An-hsiang
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p. 1516 - 1522
(2007/10/02)
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- Cross-Coupling Reaction of tert-Alkyl halides with Grignard Reagents in Dichloromethane as a Non-Lewis Basic Medium
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In dichloromethane as a non-Lewis basic solvent, 1-haloadamantane 1 underwent a cross-coupling reaction with Grignard reagents to give bridgehead-substituted products 3-16 in moderate yields.In this case the same kind of halogen in both 1 and a Grignard reagent was favored; if not, functional exchange (i.e., 1a to 1c) occurred first.The reaction using 5-hexenylmagnesium bromide as a radical probe afforded uncyclized/cyclized coupling products in a 6/4 ratio.These fact suggested the significant participation of the single-electron-transfer process in these reactions.The present method could be extended to tert-butylation with some Grignard reagents.Interestingly, 1,3-dichloro-3-methylbutane coupled with butylmagnesium chloride selectively at the tertiary position. for the above displacement reaction of 1, an organozinc was also found to be effective.
- Ohno, Masatomi,Shimizu, Kazuo,Ishizaki, Kenichi,Sasaki, Tadashi,Eguchi, Shoji
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p. 729 - 733
(2007/10/02)
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- PHOTOCHEMICAL GENERATION OF ALIPHATIC RADICALS FROM BENZOPHENONE OXIME ESTERS: SIMPLE SYNTHESIS OF ALKYLBENZENES AND ALKYLPYRIDINES
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Photolysis of benzophenone oxime esters, prepared with aliphatic carboxylic acids and benzophenone oxime, in benzene and pyridine generates various primary, secondary and tertiary aliphatic radicals selectively, and corresponding alkylbenzenes and alkylpyridines are produced in good yields, respectively.
- Hasebe, Masato,Tsuchiya, Takashi
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p. 3239 - 3242
(2007/10/02)
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- Direct Clay-Catalyzed Friedel-Crafts Arylation and Chlorination of the Hydrocarbon Adamantane
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Multiple chlorinations and arylations at the tertiary positions of adamantane are promoted by FeCl3-doped K10 montmorillonite in CCl4 or in aromatic solvents.The process, remarkably easy implement, can be tailored to selective formation of monosubstituted 1-adamantyl derivatives or 1,3-disubstituted adamantanes.The process achieves alkylation at the meta- and para-positions of toluene leading to a purely statistical distribution and displays no substrate specificity in competition experiments between toluene and benzene.
- Chalais, Stephane,Cornelis, Andre,Gerstmans, Andre,Kolodziejski, Waclaw,Laszlo, Pierre,et al.
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p. 1196 - 1203
(2007/10/02)
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- REACTIONS OF ADAMANTYL NITRATES WITH AROMATIC COMPOUNDS.
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It has been shown to be possible to use adamantyl nitrates in the synthesis of mono- and diaryladamantanes.The effects of substituents and the acidity of the medium on the yields of reaction products have been studied.
- Moiseev, I. K.,Doroshenko, R. I.
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p. 1067 - 1069
(2007/10/02)
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- Synthesis of Adamantane Derivatives. 59. Reactions of Some Electrophilic Adamantane Derivatives with Unsaturated Organosilanes
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1-Adamantyl acetate (5) and 1-adamantyl silyl ether (12) react with unsaturated organosilanes exactly as the chloride 1 does; the reactions of 5 catalyzed by trimethylsilyl triflate and of 12 catalyzed by TiCl4 with 6 and 7 give the corresponding adamantane-substituted products.Under AlCl3-catalyzed conditions, the reactions of 1-adamantylcarbinyl chloride (17) with 6 and 7 give the products which have a homoadamantane skeleton.Interestingly, the reactions of 1-adamantanecarbonyl chloride (22) with α,β- and β,γ-unsaturated silanes proceed smoothly at -78 deg C (TiCl4) or at room temperature (ZnCl2) while the competitive decarbonylation scarcely takes place.Furthermore, the reactions of 22 with silyl enol ethers are efficiently catalyzed with normal Lewis acids such as SnCl4 to give C-adamantanecarbonylated products.Some adamantane-substituted unsaturated silanes are acetylated under the conditions employed for 22 to give structurally related adamantane derivatives.The aldehyde (53) and ketone (54) show different reactivity to the unsaturated organosilanes; the former reacts with 6, 7, and 25 as usual, but the latter does not.
- Sasaki, Tadashi,Nakanishi, Akira,Ohno, Masatomi
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p. 3219 - 3224
(2007/10/02)
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- Electrophilic Aromatic Substitution. Part 30. The Effects of the p-Bicyclooctan-1-yl, Adamantan-1-yl, exo-and endo-Norbornan-2-yl,and Neopentyl Substituents in Detritiation. Steric Acceleration of Hyperconjugation
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Rate coefficients have been measured for detritiation of compounds (p-3H)C6H4R by anhydrous trifluoracetic acid at 70 deg C, and lead to the following partial rate factors(R=): bicyclooctan-1-yl, 2650; adamantan-1-yl, 2000; exo-norbornan-2-yl, 175
- Archer, William J.,Morteza, A. Hossaini,Taylor, Roger
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p. 181 - 186
(2007/10/02)
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- Rearrangement of 1-Azidoadamantane to 3-Aryl-4-azahomoadamantane in the Presence of Aluminum Chloride and Aromatic Substrates
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Reaction of 1-azidoadamantane (1) with aromatic substrates in the presence of aluminum chloride at 80 deg C for 1.25 h gave the corresponding 3-aryl-4-azahomoadamantane (2) in >90 percent yield.The reaction of 1 to 2 represents the first report of intermolecular aminoalkylation of aromatics in the benzene series, presumably from an imine intermediate.At 18 deg C, only 3-hydroxy-4-azahomoadamantane is obtained.Addition of water to the reaction system at 80 deg C yielded 1-phenyladamantane (4) as the major product.Mechanistic features are treated.
- Margosian, Daniel,Kovacic, Peter
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p. 877 - 880
(2007/10/02)
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