66821-19-0

Upstream product

• 623-12-1 4-chloromethoxybenzene 
• 97674-02-7 tributyl(1-ethoxyvinyl)stannane 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 109-92-2 ethyl vinyl ether 
• 696-62-8 para-iodoanisole 
• 857590-90-0 1-(1-ethoxy-2-chloro-ethyl)-4-methoxy-benzene 
• 64-17-5 ethanol 
• 141-52-6 sodium ethanolate 

Downstream Products

• 67233-95-8 α-methyl-p-methoxybenzyl ethyl ether 
• 1515-95-3 p-ethylanisole 
• 100-06-1 1-(4-methoxyphenyl)ethanone 

Relevant academic research and scientific papers

Catalyst-Controlled Chemodivergent Reactions of 2-Pyrrolyl-α-diazo-β-ketoesters and Enol Ethers: Synthesis of 1,2-Dihydrofuran Acetals and Highly Substituted Indoles

A catalyst-controlled, chemodivergent reaction of pyrrolyl-α-diazo-β-ketoesters with enol ethers is reported. While Cu(II) catalysts selectively promoted a [3 + 2] cycloaddition to provide pyrrolyl-substituted 2,3-dihydrofuran (DHF) acetals, dimeric Rh(II) catalysts afforded 6-hydroxyindole-7-carboxylates via an unreported [4 + 2] benzannulation. The choice of enol ether proved to be crucial in determining both regioselectivity and yield of the respective products (up to 91% yield for Cu(II) and 82% for Rh(II) catalysis). Furthermore, the DHF acetals were shown to serve as precursors to 7-hydroxyindole-6-carboxylates (isomeric to the indoles formed from Rh) and highly substituted furans in the presence of Lewis acids. Thus, from a common pyrrolyl-α-diazo-β-ketoester, up to three unique heterocyclic scaffolds can be achieved based on catalyst selection.

A novel hydrophobic fluorous ionic liquid for ligand-free Mizoroki-Heck reaction

Mizoroki-Heck reaction is carried out in a novel hydrophobic fluorous ionic liquid which was catalyzed by Pd-nanoparticles formed in situ from Pd(OAc) 2 used in the reaction. This reaction is operable under mild, aerobic, and ligand-free conditions in excellent yields. Aryl iodides, bromides as well as chlorides can be used showing its versatility. The key feature of the system is that catalyst along with ionic liquid can be reused at least five times with superior activity.

Ionic liquid-promoted, highly regioselective Heck arylation of electron-rich olefins by aryl halides

Palladium-catalyzed regioselective Heck arylation of the electron-rich olefins, vinyl ethers 1a-d, enamides 1e-g, and allyltrimethylsilane 1h, has been accomplished in imidazolium ionic liquids with a wide range of aryl bromides and iodides instead of the commonly used, but commercially unavailable and expensive, aryl triflates. The reaction proceeded with high efficiency and remarkable regioselectivity without the need for costly or toxic halide scavengers, leading exclusively to substitution by aryl groups of diverse electronic and steric properties at the olefinic carbon α to the heteroatom of 1a-g and β to the heteroatom of 1h. In contrast, the arylation reaction in molecular solvents led to mixtures of regioisomers under similar conditions. Several lines of evidence point to the unique regiocontrol stemming from the ionic environment provided by the ionic liquid that alters the reaction pathway. The chemistry provides a simple, effective method for preparing branched, arylated olefins and contributes to the extension of Heck reaction to a wider range of substrates.

Pd2(dba)3/P(i-BuNCH2CH2) 3N-catalyzed Stille cross-coupling of aryl chlorides

The Pd2(dba)3/P(i-BuNCH2CH 2)3N (1d) catalyst system is highly effective for the Stille cross-coupling of aryl chlorides with organotin compounds. This method represents only the second general method for the coupling of aryl chlorides. Other proazaphosphatranes possessing benzyl substituents also generate very active catalysts for Stille reactions. Noteworthy features of the method are: (a) commercial availability of ligand 1d, (b) the wide array of aryl chlorides that can be coupled, and (c) applicability to aryl, vinyl, and allyl tin reagents.

Highly active palladium catalysts supported by bulky proazaphosphatrane ligands for stille cross-coupling: Coupling of aryl and vinyl chlorides, room temperature coupling of aryl bromides, coupling of aryl triflates, and synthesis of sterically hindered biaryls

A family of proazaphosphatrane ligands [P(RNCH2CH 2)2N(R′NCH2CH2): R = R′ = i-Bu, 1; R = Bz, R′ = 1-Bu, 3; R = R′ = Bz, 4] for palladium-catalyzed Stille reactions of aryl chlorides is described. Catalysts derived from ligands 1 and 4 efficiently catalyze the coupling of electronically diverse aryl chlorides with an array of organotin reagents. The catalyst system based on the ligand 3 is active for the synthesis of sterically hindered biaryls (di-, tri-, and tetra-ortho substituted). The use of ligand 4 allows room-temperature coupling of aryl bromides and it also permits aryl inflates and vinyl chlorides to participate in Stille coupling.

Pd/P(t-Bu)3: A mild and general catalyst for stille reactions of aryl chlorides and aryl bromides

Pd/P(t-Bu)3 serves as an unusually reactive catalyst for Stille reactions of aryl chlorides and bromides, providing solutions to a number of long-standing challenges. An unprecedented array of aryl chlorides can be cross-coupled with a range of organotin reagents, including SnBu4. Very hindered biaryls (e.g., tetra-ortho-substituted) can be synthesized, and aryl chlorides can be coupled in the presence of aryl triflates. The method is user-friendly, since a commercially available complex, Pd(P(t-Bu)3)2, is effective. Pd/P(t-Bu)3 also functions as an active catalyst for Stille reactions of aryl bromides, furnishing the first general method for room-temperature cross-couplings.

The first general method for Stille cross-couplings of aryl chlorides

A 'one-two punch' comprising two commercially available reagents, PtBu3 and CsF, provides a practical and general solution for a long-standing limitation of the Stille reaction - the inability to couple inexpensive and readily available aryl chlorides [Eq. (1); R1 = OMe, NH2, o-Me, etc.; R = vinyl, allyl, Ph, Bu, etc.].