408492-27-3Relevant academic research and scientific papers
Design and Synthesis of Tunable Ligands with 4,4′-Bipyridyl as an Electron-Accepting Unit and Their Rhenium Complexes
Kamatsuka, Takuto,Shinokubo, Hiroshi,Miyake, Yoshihiro
, p. 3429 - 3434 (2017)
We have designed and prepared a series of rhenium complexes with 4,4′-bipyridyl as an electron-accepting unit. Electrochemical studies revealed that oxidation and reduction of these complexes occurred on the rhenium center and the 4,4′-bipyridyl skeleton, respectively. The redox potentials of the rhenium complexes are controllable by tuning the substituents on the 4,4′-bipyridyl skeleton and the coordinating groups to the rhenium center. We have also examined the reactivity of the rhenium complexes in electrochemical and photochemical CO2 reduction.
Metal-Templated Oligomeric Macrocyclization via Coupling for Metal-Doped π-Systems
Ikemoto, Koki,Isobe, Hiroyuki,Matsuno, Taisuke,Miyachi, Akira,Muto, Hitomi,Sasakawa, Hiroaki,Yang, Seungmin
supporting information, p. 15017 - 15021 (2021/09/30)
A method for the synthesis of metal-doped aromatic macrocycles has been developed. The method, i.e., metal-templated oligomeric macrocyclization via coupling, adopts Ni as the template and assembles five pyridine units via a Ni-mediated coupling reaction
Understanding the Activation of Air-Stable Ir(COD)(Phen)Cl Precatalyst for C-H Borylation of Aromatics and Heteroaromatics
Slack, Eric D.,Colacot, Thomas J.
supporting information, p. 1561 - 1565 (2021/02/20)
A newly developed robust catalyst [Ir(COD)(Phen)Cl] (A) was used for the C-H borylation of three dozen aromatics and heteroaromatics with excellent yield and selectivity. Activation of the catalyst was identified by the use of catalytic amounts of water, alcohols, etc., when B2pin2 was used in noncoordinating solvents, while for THF catalytic use of HBpin was required. The results were on par with the in situ based expensive system [Ir(OMe)(COD)]2/dtbbpy or Me4Phen.
TRI-SUBSTITUTED ARYL AND HETEROARYL DERIVATIVES AS MODULATORS OF PI3-KINASE AND AUTOPHAGY PATHWAYS
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Paragraph 0342, (2019/11/04)
The present disclosure relates to tri-substituted aryl and heteroaryl derivatives, pharmaceutical compositions containing them, and methods of using them, including methods for modulating autophagy or preventing, reversing, slowing or inhibiting the PI3K-AKT-MTOR pathway, and methods of treating diseases that are associated with autophagy or the PI3K-AKT-MTOR pathway.
NNB-type tridentate boryl ligands enabling a highly active iridium catalyst for C–H borylation
Ding, Siyi,Wang, Linghua,Miao, Zongcheng,Li, Pengfei
, (2019/04/30)
Boryl ligands play a very important role in catalysis because of their very high electron-donating property. In this paper, NNB-type boryl anions were designed as tridentate ligands to promote aryl C–H borylation. In combination with [IrCl(COD)]2/su
Synthesis process of 2,6-dichloropyridine-4-boracic acid pinacol ester
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Paragraph 0016; 0019; 0023; 0027, (2018/06/26)
The invention discloses a synthesis process of 2,6-dichloropyridine-4-boracic acid pinacol ester. 2,6-dichloropyridine is used as raw materials; under the existence of 2,2,6,6-lithium tetramethylpiperidide or Grignard reagents, protons are selectively removed at low temperature; a boron halide reagent is added; then, pinacol is added for treatment to obtain the 2,6-dichloropyridine-4-boracic acidpinacol ester. The method has the advantages that the operation steps are short; 2,2,6,6-tetramethylpiperidide can be easily recovered and utilized; 4-site products can be obtained at high selectivity; potential practical values are realized.
Trimethylphosphate as a Methylating Agent for Cross Coupling: A Slow-Release Mechanism for the Methylation of Arylboronic Esters
He, Zhi-Tao,Li, Haoquan,Haydl, Alexander M.,Whiteker, Gregory T.,Hartwig, John F.
supporting information, p. 17197 - 17202 (2018/12/14)
A methyl group on an arene, despite its small size, can have a profound influence on biologically active molecules. Typical methods to form a methylarene involve strong nucleophiles or strong and often toxic electrophiles. We report a strategy for a new, highly efficient, copper and iodide co-catalyzed methylation of aryl- and heteroarylboronic esters with the mild, nontoxic reagent trimethylphosphate, which has not been used previously in coupling reactions. We show that it reacts in all cases tested in yields that are higher than those of analogous copper-catalyzed reactions of MeOTs or MeI. The combination of C-H borylation and this methylation with trimethylphosphate provides a new approach to the functionalization of inert C-H bonds and is illustrated by late-stage methylation of four medicinally active compounds. In addition, reaction on a 200 mmol scale demonstrates reliability of this method. Mechanistic studies show that the reaction occurs by a slow release of methyl iodide by reaction of PO(OMe)3 with iodide catalyst, rather than the typical direct oxidative addition to a metal center. The low concentration of the reactive electrophile enables selective reaction with an arylcopper intermediate, rather than nucleophilic groups on the arylboronate, and binding of tert-butoxide to the boronate inhibits reaction of the electrophile with the tert-butoxide activator to form methyl ether.
METHODS FOR FORMING SATURATED (HETERO)CYCLIC BORYLATED HYDROCARBONS AND RELATED COMPOUNDS
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Paragraph 0052, (2018/03/25)
The disclosure relates to methods for forming at least partially saturated cyclic and heterocyclic borylated hydrocarbons, as well as related compounds, which can be precursor compounds in the synthesis of any of a variety of pharmaceutical or medicinal compounds with a desired structure and/or stereochemistry for drug synthesis or drug candidate evaluation. The methods generally include reduction of an unsaturated cyclic or heterocyclic borylated hydrocarbon having a boron-containing substituent at an sp2-carbon, where such reduction converts the sp2-carbon to an sp3-carbon at the point of attachment of the boron-containing substituent. The methods can exhibit a selectivity for syn-addition during reduction, which can provide stereospecific products, such as when the unsaturated cyclic or heterocyclic reactant is multiply substituted with boron groups and/or other functional groups.
Iridium-bipyridine periodic mesoporous organosilica catalyzed direct C-H borylation using a pinacolborane
Maegawa, Yoshifumi,Inagaki, Shinji
supporting information, p. 13007 - 13016 (2016/01/09)
Heterogeneous catalysis for direct C-H borylation of arenes and heteroarenes in the combination of iridium (Ir) complex fixed on periodic mesoporous organosilica containing bipyridine ligands within the framework (Ir-BPy-PMO) and pinacolborane (HBpin) is reported. Ir-BPy-PMO showed higher catalytic activity toward the borylation of benzene with inexpensive HBpin compared to expensive bis(pinacolato)diboron (B2pin2). The precatalyst could be handled without the use of a glove box. The catalyst was easily recovered from reaction mixtures by simple filtration under air. The recovered catalyst still showed good catalytic activity for at least three more times for the borylation of benzene. A variety of arenes and heteroarenes were successfully borylated with high boron efficiency by Ir-BPy-PMO using HBpin, whereas almost no activity was observed for borylation of some heteroarenes with B2pin2. The system using Ir-BPy-PMO and HBpin was also utilized in syntheses of multi-boronated thiophene-based building blocks containing ladder-, acenefused-, and fused-thiophene skeletons. The combination of a stable and reusable solid catalyst and inexpensive HBpin is expected to be superior to conventional approaches for the development of industrial applications.
Harnessing C-H Borylation/Deborylation for Selective Deuteration, Synthesis of Boronate Esters, and Late Stage Functionalization
Kallepalli, Venkata A,Gore, Kristin A.,Shi, Feng,Sanchez, Luis,Chotana, Ghayoor A.,Miller, Susanne L.,Maleczka, Robert E.,Smith, Milton R.
, p. 8341 - 8353 (2015/09/02)
Ir-catalyzed deborylation can be used to selectively deuterate aromatic and heteroaromatic substrates. Combined with the selectivities of Ir-catalyzed C-H borylations, uniquely labeled compounds can be prepared. In addition, diborylation/deborylation reactions provide monoborylated regioisomers that complement those prepared by C-H borylation. Comparisons between Ir-catalyzed deborylations and Pd-catalyzed deborylations of diborylated indoles described by Movassaghi are made. The Ir-catalyzed process is more effective for deborylating aromatics and is generally more effective in the monodeborylation of diborylated thiophenes. These processes can be applied to complex molecules such as clopidogrel.
