99142-77-5

Upstream product

• 1067-74-9 Methyl diethylphosphonoacetate 
• 100-06-1 1-(4-methoxyphenyl)ethanone 
• 88738-78-7 bis-(2,2,2-trifluoroethyl)(methoxycarbonylmethyl)phosphonate 
• 623-43-8 crotonic acid methyl ester 
• 98-68-0 4-methoxy-phenyl-sulphonyl chloride 
• 1029612-16-5 (E)-methyl 3-(p-toluenesulfonyloxy)but-2-enoate 
• 13139-86-1 4-methoxyphenyl magnesium bromide 
• 623-43-8 methyl crotonate 
• 696-62-8 para-iodoanisole 
• 1712-69-2 1-isopropenyl-4-methoxybenzene 
• 93296-09-4 4-methoxyphenylzinc chloride 
• 5720-07-0 4-methoxyphenylboronic acid 
• 67-56-1 methanol 
• 123559-08-0 2-(4-Methoxy-phenyl)-4,4-bis-methylsulfanyl-but-3-en-2-ol 

Downstream Products

• 143704-81-8 methyl 4-bromo-3-(4-methoxyphenyl)-2-butenoate 
• 136762-97-5 4-(4-hydroxyphenyl)-5-[(Z)-(4-hydroxyphenyl)methylidene]furan-2-one 
• 3516-65-2 4-(4-methoxyphenyl)furan-2(5H)-one 
• 216227-78-0 4-(4-methoxyphenyl)-5-[(Z)-(4-methoxyphenyl)methylidene]furan-2-one 
• 136762-98-6 (Z)-4-(4-hydroxyphenyl)-5-(4-methoxybenzylidene)furan-2(5H)-one 
• 1608121-21-6 (Z)-5-(4-hydroxy-3-(3-methylbut-2-en-1-yl)benzylidene)-4-(4-hydroxyphenyl)furan-2(5H)-one 
• 1608121-24-9 (Z)-5-((2,2-dimethylchroman-6-yl)methylene)-4-(4-hydroxyphenyl)furan-2(5H)-one 
• 133678-75-8 methyl (Z)-3-(3-methoxyphenyl)-3-methylacrylate 
• 143704-87-4 4-(4-methoxyphenyl)-N-phenylpyrrolone 

Relevant academic research and scientific papers

Dramatic Effect of γ-Heteroatom Dienolate Substituents on Counterion Assisted Asymmetric Anionic Amino-Cope Reaction Cascades

We report a dramatic effect on product outcomes of the lithium ion enabled amino-Cope-like anionic asymmetric cascade when different γ-dienolate heteroatom substituents are employed. For dienolates with azide, thiomethyl, and trifluoromethylthiol substituents, a Mannich/amino-Cope/cyclization cascade ensues to form chiral cyclohexenone products with two new stereocenters in an anti-relationship. For fluoride-substituted nucleophiles, a Mannich/amino-Cope cascade proceeds to afford chiral acyclic products with two new stereocenters in a syn-relationship. Bromide- and chloride-substituted nucleophiles appear to proceed via the same pathway as the fluoride albeit with the added twist of a 3-exo-trig cyclization to yield chiral cyclopropane products with three stereocenters. When this same class of nucleophiles is substituted with a γ-nitro group, the Mannich-initiated cascade is now diverted to a β-lactam product instead of the amino-Cope pathway. These anionic asymmetric cascades are solvent- and counterion-dependent, with a lithium counterion being essential in combination with etheral solvents such as MTBE and CPME. By altering the geometry of the imine double bond from E to Z, the configurations at the R1 and X stereocenters are flipped. Mechanistic, computational, substituent, and counterion studies suggest that these cascades proceed via a common Mannich-product intermediate, which then proceeds via either a chair (X = N3, SMe, or SCF3) or boat-like (X = F, Cl, or Br) transition state to afford amino-Cope-like products or β-lactam in the case of X = NO2.

Copper-Catalyzed 1,2-Methoxy Methoxycarbonylation of Alkenes with Methyl Formate

Reported here is a copper-catalyzed 1,2-methoxy methoxycarbonylation of alkenes by an unprecedented use of methyl formate as a source of both the methoxy and the methoxycarbonyl groups. This reaction transforms styrene and its derivatives into value-added β-methoxy alkanoates and cinnamates, as well as medicinally important five-membered heterocycles, such as functionalized tetrahydrofurans, γ-lactones, and pyrrolidines. A ternary β-diketiminato-CuI-styrene complex, fully characterized by NMR spectroscopy and X-ray crystallographic analysis, is capable of catalyzing the same transformation. These findings suggest that pre-coordination of electron-rich alkenes to copper might play an important role in accelerating the addition of nucleophilic radicals to electron-rich alkenes, and could have general implications in the design of novel radical-based transformations.

Microwave-Assisted Synthesis of Phenylpropanoids and Coumarins: Total Synthesis of Osthol

Herein we describe a one-pot microwave-assisted method for the synthesis of cinnamic acid and coumarin derivatives. The synthesis begins with an aldehyde synthon, and the chosen reaction conditions determine whether a cinnamic acid or coumarin derivative is formed. A regioselective Claisen rearrangement was also efficiently incorporated into the synthetic sequence to further increase the complexity of the product. Notably, this approach provides high product yields and selectivities without the need of a phenol protecting group.

Efficient, collective synthesis and nitric oxide inhibitory activity of rubrolides E, F, R, S and their derivatives

An efficient first synthesis of biologically significant natural butenolides, rubrolides F (1f), R (1r), S (1s) & its 7″,8″-didehydro derivative (1sa), and 3″-bromo rubrolide (1fa) along with the synthesis of rubrolide E (1e) and its di-O-methyl derivative (1ea) is accomplished in a collective fashion from commercially available and inexpensive precursors in overall yields of 14–48.5%. Key features are Wittig-Horner reaction, SeO2-induced tandem allylic hydroxylation/intramolecular cyclization and Knoevenagel condensation. Next, in their inhibitory activity towards nitric oxide (NO) production in lipopolysaccharide-induced RAW 264.7 macrophages as an indicator of anti-inflammatory activity, all compounds displayed good inhibitory activity in a concentration-dependent manner. None of the compound exhibited notable cytotoxicity at the highest concentration (10?μM) and IC50values are found in the range from 8.53 to 17.85?μM.

Synthetic method for rubrolide compounds E, F, R, S and their derivatives

Rubrolide F (compound 1f), R (compound 1r), and S (compound 1s), which are biological important natural butenolides, 7andPrime;,8andPrime;-didihydro derivatives (compound 1sa) thereof, 3andPrime; -bromorubrolide (compound 1fa), rubrolide E (compound 1e) and di-O-methyl derivatives thereof (compound 1ea) can be industrially obtained and are effectively synthesized with the overall yield of 14-48.5% from low-priced precursors. The rubrolide compounds can be synthesized through a Knoevenagel condensation reaction after a Wittig-Horner reaction and SeO_2-induced tandem allylic hydroxylation/intramolecular cyclization for preparing butenolide rings and a rubrolide cores structure.COPYRIGHT KIPO 2017

DMAP-Catalyzed [4 + 2] Cycloaddition of α,β-Unsaturated Carboxylic Acids with Ketones for Synthesis of α,β-Unsaturated δ-Lactones

The DMAP-catalyzed [4 + 2] cycloaddition of α,β-unsaturated carboxylic acids with ketones furnishing α,β-unsaturated δ-lactones in good yields (up to 80%) is described, which is the first example of remote γ-C(sp3)-H activation of α,β-unsaturated carboxylic acids facilitated by DMAP, a pyridine-based catalyst. Copyright

Highly efficient synthesis of chiral aromatic ketones: Via Rh-catalyzed asymmetric hydrogenation of β,β-disubstituted enones

A succinct and efficient protocol was developed for the synthesis of chiral aromatic ketones via asymmetric hydrogenation of β,β-disubstituted enones with rhodium catalysts based on chiral bisphosphine thiourea ligands. A series of substrates (17 examples) was smoothly catalyzed to afford the corresponding chiral aromatic ketones in high conversions (>99%) with excellent enantioselectivities (up to 96% ee).

Rhodium-Catalyzed Asymmetric Hydrogenation of α,β-Unsaturated Carbonyl Compounds via Thiourea Hydrogen Bonding

The strategy of secondary interaction enables enantioselectivity for homogeneous hydrogenation. By introducing hydrogen bonding of substrates with thiourea from the ligand, α,β-unsaturated carbonyl compounds, such as amides and esters, are hydrogenated wi

Cobalt nanoparticles supported on ionic liquid-functionalized multiwall carbon nanotubes as an efficient and recyclable catalyst for Heck reaction

A novel and environmentally friendly cobalt nanoparticle catalyst supported on ionic liquid-functionalized multiwall carbon nanotubes was successfully prepared and evaluated as a heterogeneous catalyst for the Mizoroki-Heck reaction. Several reaction parameters, including type and amount of solvent and base, were evaluated. This nanocatalyst could also be recovered and reused at least six times without any discernible decrease in its catalytic activity.

Selective reactivity of electron-rich aryl iodides in the Heck arylation of disubstituted alkenes catalyzed by palladium-arylurea complexes

A catalyst consisting of 1 mol % of the 1:2 complex of Pd(OAc)2 with N-(4-carbethoxyphenyl)urea promotes the Heck arylation of 2- or 3-substituted, conjugated esters, nitriles, aldehydes, and ketones (an uncharacteristically broad range of substrates), but only with electron-rich aryl iodides (an uncharacteristically narrow range of halides).