24306-23-8

Usage

InChI:InChI=1/C12H16O2/c1-10-6-8-11(9-7-10)4-3-5-12(13)14-2/h6-9H,3-5H2,1-2H3

Upstream product

• 186581-53-3 diazomethane 
• 4521-22-6 4-(4-methylphenyl)butyric acid 
• 104-87-0 4-methyl-benzaldehyde 
• 52693-87-5 4-methylbenzaldehyde hydrazone 
• 292638-85-8 acrylic acid methyl ester 
• 622-97-9 1-ethenyl-4-methylbenzene 
• 2365-48-2 Methyl thioglycolate 
• 108-88-3 toluene 
• 4619-20-9 3-(4-methylbenzoyl)propionic acid 
• 106-42-3 para-xylene 
• 67-56-1 methanol 

Downstream Products

• 22184-00-5 2-(methyl-5-(4-methylphenyl))-2-pentanol 
• 1332954-73-0 (E)-6-(p-tolyl)hex-3-en-1-ol 
• 81036-83-1 4-(p-tolyl)butanal 
• 98453-65-7 C₂₀H₂₂N₂O₂S 
• 22824-34-6 1,2,3,4-tetrahydro-1,1,7-trimethyl-naphthalene 

Relevant academic research and scientific papers

Ligand-controlled cobalt-catalyzed remote hydroboration and alkene isomerization of allylic siloxanes

The Co-catalyzed remote hydroboration and alkene isomerization of allylic siloxanes were realized by a ligand-controlled strategy. The remote hydroboration with dcype provided borylethers, while xantphos favored the formation of silyl enol ethers.

An Iron-Mesoionic Carbene Complex for Catalytic Intramolecular C-H Amination Utilizing Organic Azides

The synthesis of N-heterocycles is of paramount importance for the pharmaceutical industry. They are often synthesized through atom economic and environmentally unfriendly methods, generating significant waste. A less explored, but greener, alternative is

Enantioselective C-H Amination Catalyzed by Nickel Iminyl Complexes Supported by Anionic Bisoxazoline (BOX) Ligands

The trityl-substituted bisoxazoline (TrHBOX) was prepared as a chiral analogue to a previously reported nickel dipyrrin system capable of ring-closing amination catalysis. Ligand metalation with divalent NiI2(py)4 followed by potassium graphite reduction afforded the monovalent (TrHBOX)Ni(py) (4). Slow addition of 1.4 equiv of a benzene solution of 1-adamantylazide to 4 generated the tetrazido (TrHBOX)Ni(κ2-N4Ad2) (5) and terminal iminyl adduct (TrHBOX)Ni(NAd) (6). Investigation of 6 via single-crystal X-ray crystallography, NMR and EPR spectroscopies, and computations revealed a Ni(II)-iminyl radical formulation, similar to its dipyrrinato congener. Complex 4 exhibits enantioselective intramolecular C-H bond amination to afford N-heterocyclic products from 4-aryl-2-methyl-2-azidopentanes. Catalytic C-H amination occurs under mild conditions (5 mol % catalyst, 60 °C) and provides pyrrolidine products in decent yield (29%-87%) with moderate ee (up to 73%). Substrates with a 3,5-dialkyl substitution on the 4-aryl position maximized the observed enantioselectivity. Kinetic studies to probe the reaction mechanism were conducted using 1H and 19F NMR spectroscopies. A small, intermolecular kinetic isotope effect (1.35 ± 0.03) suggests an H-atom abstraction step with an asymmetric transition state while the reaction rate is measured to be first order in catalyst and zeroth order in substrate concentrations. Enantiospecific deuterium labeling studies show that the enantioselectivity is dictated by both the H-atom abstraction and radical recombination steps due to the comparable rate between radical rotation and C-N bond formation. Furthermore, the competing elements of the two-step reaction where H-removal from the pro-R configuration is preferred while the preferential radical capture occurs with the Si face of the carboradical likely lead to the diminished ee observed, as corroborated by theoretical calculations. Based on these enantio-determining steps, catalytic enantioselective synthesis of 2,5-bis-tertiary pyrrolidines is demonstrated with good yield (50-78%) and moderate ee (up to 79%).

Copper-Catalyzed Conjugate Addition of Carbonyls as Carbanion Equivalent via Hydrazones

Copper-catalyzed conjugate addition is a classic method for forming new carbon-carbon bonds. However, copper has never showed catalytic activity for umpolung carbanions in hydrazone chemistry. Herein, we report a facile conjugate addition of hydrazone catalyzed by readily available copper complexes at room temperature. The employment of mesitylcopper(I) and electron-rich phosphine bidentate ligand is a key factor affecting reactivity. The reaction allows various aromatic hydrazones to react with diverse conjugated compounds to produce 1,4-adducts in yields of about 20 to 99%.

Catalytic C-H Amination Mediated by Dipyrrin Cobalt Imidos

Reduction of (ArL)CoIIBr (ArL = 5-mesityl-1,9-(2,4,6-Ph3C6H2)dipyrrin) with potassium graphite afforded the novel CoI synthon (ArL)CoI. Treatment of (ArL)CoI with a stoichiometric amount of various alkyl azides (N3R) furnished three-coordinate CoIII alkyl imidos (ArL)Co(NR), as confirmed by single-crystal X-ray diffraction (R: CMe2Bu, CMe2(CH2)2CHMe2). The exclusive formation of four-coordinate cobalt tetrazido complexes (ArL)Co(κ2-N4R2) was observed upon addition of excess azide, inhibiting any subsequent C-H amination. However, when a weak C-H bond is appended to the imido moiety, as in the case of (4-azido-4-methylpentyl)benzene, intramolecular C-H amination kinetically outcompetes formation of the corresponding tetrazene species to generate 2,2-dimethyl-5-phenylpyrrolidine in a catalytic fashion without requiring product sequestration. The imido (ArL)Co(NAd) exists in equilibrium in the presence of pyridine with a four-coordinate cobalt imido (ArL)Co(NAd)(py) (Ka = 8.04 M-1), as determined by 1H NMR titration experiments. Kinetic studies revealed that pyridine binding slows down the formation of the tetrazido complex by blocking azide coordination to the CoIII imido. Further, (ArL)Co(NR)(py) displays enhanced C-H amination reactivity compared to that of the pyridine-free complex, enabling higher catalytic turnover numbers under milder conditions. The mechanism of C-H amination was probed via kinetic isotope effect experiments [kH/kD = 10.2(9)] and initial rate analysis with para-substituted azides, suggesting a two-step radical pathway. Lastly, the enhanced reactivity of (ArL)Co(NR)(py) can be correlated to a higher spin-state population, resulting in a decreased crystal field due to a geometry change upon pyridine coordination.

BEXAROTENE DERIVATIVES AND THEIR USE IN TREATING CANCER

This disclosure relates to compositions and methods for treating cancer. Specifically, this disclosure relates to bexarotene derivatives, methods for treating cancer, autoimmune disorders, and/or skin dermatitis, and/or methods for increasing peripheral blood counts and/or improving immune system function.

Reductive C-C Coupling by Desulfurizing Gold-Catalyzed Photoreactions

[Au2(μ-dppm)2]Cl2-mediated photocatalysis reactions are usually initiated by ultraviolet A (UVA) light; herein, an unreported system using blue light-emitting diodes (LEDs) as excitation light source was found. The red shift of the absorption wavelength originates from the combination of [Au2(μ-dppm)2]Cl2 and ligand (Ph3P or mercaptan). On the basis of this finding, a gold-catalyzed reductive desulfurizing C-C coupling of electrophilic radicals and styrenes mediated by blue LEDs is presented, a coupling which cannot be efficiently accessed by previously reported methods. This mild and highly efficient C-C bond formation strategy uses mercaptans both as electron-deficient alkyl radical precursor as well as the hydrogen source. Two examples of amino acids have also been modified by using this strategy. Moreover, this methodology could be applied in polymer synthesis. Gram-scale synthesis and mechanistic insights into this transformation are also presented.

A metal-free desulfurizing radical reductive C-C coupling of thiols and alkenes

An intermolecular reductive C-C coupling of electrophilic alkyl radicals and alkenes has been developed. Thiols were used as both hydrogen-donating reagents and alkyl radical precursors in the presence of triethyl phosphite and radical initiator. A wide range of alkenes, including styrenes, and aliphatic olefins were well tolerated in this transformation. Mechanistic studies indicated that a phosphite promoted radical desulfurization of thiols to access electrophilic alkyl radicals and a radical chain propagation process may be involved in this transformation.

Metal-Free Enantioselective Oxidative Arylation of Alkenes: Hypervalent-Iodine-Promoted Oxidative C?C Bond Formation

The enantioselective oxyarylation of (E)-6-aryl-1-silyloxylhex-3-ene was achieved using a lactate-based chiral hypervalent iodine(III) reagent in the presence of boron trifluoride diethyl etherate. The silyl ether promotes the oxidative cyclization, and enhances the enantioselectivity. In addition, the corresponding aminoarylation was achieved.

Compositions and methods for treatment of hyperproliferative diseases

The invention relates to compositions comprising a retinoid X receptor agonist and an agent capable of activating protein kinase A. The invention also relates to methods of treating hyperproliferative diseases by administering a retinoid X receptor agonis