780-68-7Relevant articles and documents
Air-Stable Iron-Based Precatalysts for Suzuki-Miyaura Cross-Coupling Reactions between Alkyl Halides and Aryl Boronic Esters
Wong, Alexander S.,Zhang, Bufan,Li, Bo,Neidig, Michael L.,Byers, Jeffery A.
, p. 2461 - 2472 (2021/11/01)
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.
Resolution of Vaulted Biaryl Ligands via Borate Esters of Quinine and Quinidine
Cagnon, Brian R.,Mohammadlou, Aliakbar,Wulff, William D.,Yin, Xiaopeng,Zheng, Li
, p. 10432 - 10450 (2020/09/23)
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.
Preparation method of 1-phenyl adamantane and obtained 1-phenyl adamantane
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Paragraph 0042-0060; 0062-0065, (2020/08/02)
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
Adamantane-containing compound, high polymer, mixture, composition, and electronic device
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Paragraph 0236-0239; 0267-0270, (2020/02/20)
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.
Flow Friedel–Crafts alkylation of 1-adamantanol with arenes using HO-SAS as an immobilized acid catalyst
Kasakado, Takayoshi,Hyodo, Mamoru,Furuta, Akihiro,Kamardine, Aina,Ryu, Ilhyong,Fukuyama, Takahide
, p. 2253 - 2257 (2020/12/15)
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.
Rational Design of an Iron-Based Catalyst for Suzuki–Miyaura Cross-Couplings Involving Heteroaromatic Boronic Esters and Tertiary Alkyl Electrophiles
Byers, Jeffery A.,Crockett, Michael P.,Li, Bo,Wong, Alexander S.
supporting information, p. 5392 - 5397 (2020/03/04)
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.
Ni-Catalyzed Electrochemical Decarboxylative C-C Couplings in Batch and Continuous Flow
Li, Hui,Breen, Christopher P.,Seo, Hyowon,Jamison, Timothy F.,Fang, Yuan-Qing,Bio, Matthew M.
, p. 1338 - 1341 (2018/03/09)
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.
Iron-Catalyzed Suzuki-Miyaura Cross-Coupling Reactions between Alkyl Halides and Unactivated Arylboronic Esters
Crockett, Michael P.,Tyrol, Chet C.,Wong, Alexander S.,Li, Bo,Byers, Jeffery A.
supporting information, p. 5233 - 5237 (2018/09/12)
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.
Alkyl?(Hetero)Aryl Bond Formation via Decarboxylative Cross-Coupling: A Systematic Analysis
Sandfort, Frederik,O'Neill, Matthew J.,Cornella, Josep,Wimmer, Laurin,Baran, Phil S.
, p. 3319 - 3323 (2017/03/17)
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.
Initiation in Photoredox C-H Functionalization Reactions. Is Dimsyl Anion a Key Ingredient?
Budén, María E.,Bardagí, Javier I.,Puiatti, Marcelo,Rossi, Roberto A.
supporting information, p. 8325 - 8333 (2017/08/23)
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.
