Halogen—Lithium Exchange Between Substituted Dihalobenzenes and Butyllithium: Application to the Regioselective Synthesis of Functionalized Bromobenzaldehydes.

Dąbrowski, Marek; Kubicka, Joanna; Luliński, Sergiusz; Serwatowski, Janusz

doi:10.1002/chin.200542092

Cited by 3 publications

(5 citation statements)

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“…1 . Heck coupling [ 23 ] of 4-bromo-3-methoxybenzaldehyde [ 24 ] with Boc-protected 4-amino styrene in the presence of the water-soluble TPPTS catalyst proceeded in 70 % yield after purification, to give stylbene aldehyde 2 . Subsequent olefination [ 25 ] with the phosphonate 3 proceeded in 65 % yield after purification to give the bis-stylbene 4 , exclusively in the trans–trans configuration [ 26 ].…”

Section: Methodsmentioning

confidence: 99%

Intraoperative Fluorescence Imaging of Peripheral and Central Nerves Through a Myelin-Selective Contrast Agent

et al. 2012

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PurposePatients suffer from complications as a result of unintentional nerve damage during surgery. We focus on improving intraoperative visualization of nerves through the use of a targeted fluorophore and optical imaging instrumentation.ProcedureA myelin-targeting fluorophore, GE3111, was synthesized, characterized for its optical and myelin-binding properties using purified myelin basic protein, and evaluated in mice. Additionally, a compact instrument was adapted to visualize nerves.ResultsGE3111 was synthesized using a versatile methodology. Its optical properties were sensitive to the local environment both in vitro and in vivo. Following intravenous injection, central and peripheral nerves were visualized, with the kinetics of nerve uptake modifiable depending on the formulation. Fluorescence polarization showed specific and strong binding to purified myelin basic protein. Nerves were visualized in vivo using a dedicated compact imaging device requiring less than 2.5 mW/cm2 of illumination at 405 nm.ConclusionsFluorescence imaging of nerves through myelin showed a potential for use in image-guided surgery. Intraoperative nerve imaging is an example where contrast agent and instrument development come together as a result of clinical need.Electronic supplementary materialThe online version of this article (doi:10.1007/s11307-012-0555-1) contains supplementary material, which is available to authorized users.

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Section: Methodsmentioning

confidence: 99%

Intraoperative Fluorescence Imaging of Peripheral and Central Nerves Through a Myelin-Selective Contrast Agent

et al. 2012

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“…A method different from that reported in ref was used. To a solution of benzonitrile 22 (1.04 g, 4.90 mmol) in anhydrous PhMe (14 mL) at −78 °C was added 1 M DIBAL (7.35 mmol) in CH 2 Cl 2 (7.40 mL).…”

Section: Methodsmentioning

confidence: 99%

“…The reaction mixture was stirred at −78 °C for 0.5 h, warmed to room temperature, stirred for an additional 4.25 h, the reaction quenched with MeOH (4 mL), and the mixture stirred for 0.5 h. After addition of 10% H 2 SO 4 (45 mL), the resulting solution was stirred for 1.75 h and then extracted with EtOAc (100 mL, 50 mL). After solvent removal at reduced pressure, the residue was chromatographed (10 to 16% EtOAc/hexane) to give 876 mg (83%) of 23 as a white solid: mp 70–72 °C (lit . 74–76 °C); IR 2960, 1701, 1582, 1042 cm –1 ; 1 H NMR δ 4.01 (s, 3H, CH 3 ), 7.36 (dd, J = 1.8, 7.8 Hz, 1H, 6-ArH), 7.43 (d, J = 1.8 Hz, 1H, 2-ArH), 7.77 (d, J = 7.8 Hz, 1H, 5-ArH), 9.98 (s, 1H, CHO).…”

Section: Methodsmentioning

confidence: 99%

“…After solvent removal at reduced pressure, the residue was chromatographed (10 to 16% EtOAc/hexane) to give 876 mg (83%) of 23 as a white solid: mp 70−72 °C (lit. 46 74−76 °C); IR 2960, 1701, 1582, 1042 cm −1 ; 1 H NMR δ 4.01 (s, 3H, CH 3 ), 7.36 (dd,J = 1.8,7.8 Hz,1H,7.43 (d,J = 1.8 Hz,1H,7.77 (d,J = 7.8 Hz,1H,9.98 (s,1H,CHO).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Analogues of Orphan Nuclear Receptor Small Heterodimer Partner Ligand and Apoptosis Inducer (E)-4-[3-(1-Adamantyl)-4-hydroxyphenyl]-3-chlorocinnamic Acid. 2. Impact of 3-Chloro Group Replacement on Inhibition of Proliferation and Induction of Apoptosis of Leukemia and Cancer Cell Lines

et al. 2011

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The parent phenol of adapalene and its (E)-cinnamic acid analogue were found to induce cancer cell apoptosis but cause adverse systemic effects when administered to mice. In contrast, their respective 5-Cl- and 3-Cl-substituted analogues had their adverse effects mitigated without a comparable loss of cancer cell inhibitory activity. As a result, pharmacologic space in this region of the cinnamic phenyl ring scaffold was explored. Various substituents were introduced, and their effects on cancer cell proliferation and viability were evaluated. Cinnamic acids having 3-Br, CN, NO(2), NH(2), OMe, and N(3) groups had activity comparable to that of 4-[3'-(1-adamantyl)-4'-hydroxyphenyl]-3-chlorocinnamic acid. A comparative molecular field analysis study indicated that introduction of an H-bond acceptor at position 3 of the central phenyl ring would favor inhibition of leukemia cell viability, and docking suggested its hydrogen bonding with a polar group in a small heterodimer partner homology model. The 3-CN, NO(2), NH(2), and OH analogues also inhibited MMTV-Wnt1 murine mammary stem cell viability.

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“…Characterization in agreement with literature. 26 The Z-isomer was isolated in small amounts from a mixture of isomers through normal-phase flash chromatography on silica with 10% ethyl acetate in hexane. 1 H NMR (400 MHz, CD 3 CN) δ 7.59 (ddd, J = 8.6, 7.3, 0.6 Hz, 1H), 7.46 (dd, J = 8.6, 1.3 Hz, 1H), 6.86 (s, 1H), 5.70 (s, 1H), 2.92 (d, J = 4.4 Hz, 3H).…”

Section: General Procedures a For The Formation Of The Benzaldehydesmentioning

confidence: 99%

Process Development for a 1H-Indazole Synthesis Using an Intramolecular Ullmann-Type Reaction

2023

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Within the scope of developing a new route to an active pharmaceutical ingredient intermediate, we had need of a fluorinated indazole. Although an established route was in place, it was undesirable due to safety and selectivity concerns. A concise and improved route was developed to form the desired indazole, which takes advantage of an electronically directed metalation/formylation sequence followed by condensation with methyl hydrazine to form a hydrazone and culminates in a copper-catalyzed intramolecular Ullmann cyclization. The Ullmann reaction was plagued with difficulties ranging from poor reactivity to thermal hazard concerns, but use of high-throughput screening, statistical modeling, and an unusual isolation method for fine chemicals, safe and optimal conditions were found that produce high-purity isolated material in excellent yields at a laboratory scale.

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Halogen—Lithium Exchange Between Substituted Dihalobenzenes and Butyllithium: Application to the Regioselective Synthesis of Functionalized Bromobenzaldehydes.

Cited by 3 publications

References 1 publication

Intraoperative Fluorescence Imaging of Peripheral and Central Nerves Through a Myelin-Selective Contrast Agent

Intraoperative Fluorescence Imaging of Peripheral and Central Nerves Through a Myelin-Selective Contrast Agent

Analogues of Orphan Nuclear Receptor Small Heterodimer Partner Ligand and Apoptosis Inducer (E)-4-[3-(1-Adamantyl)-4-hydroxyphenyl]-3-chlorocinnamic Acid. 2. Impact of 3-Chloro Group Replacement on Inhibition of Proliferation and Induction of Apoptosis of Leukemia and Cancer Cell Lines

Process Development for a 1H-Indazole Synthesis Using an Intramolecular Ullmann-Type Reaction

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