141885-87-2

Upstream product

• 103-26-4 Methyl cinnamate 
• 6921-34-2 benzylmagnesium chloride 
• 100-44-7 benzyl chloride 
• 103-26-4 methyl cinnamate 

Downstream Products

• 14944-26-4 3-phenyl-1-tetralone 
• 4374-49-6 3-benzyl-3-phenylpropionic acid 
• 92962-43-1 4-benzyl-3,4-dihydroquinolin-2(1H)-one 

Relevant academic research and scientific papers

Ruthenium-catalyzed intramolecular arene C(sp2)-H amidation for synthesis of 3,4-dihydroquinolin-2(1 H)-ones

We report the [Ru(p-cymene)(l-proline)Cl] ([Ru1])-catalyzed cyclization of 1,4,2-dioxazol-5-ones to form dihydroquinoline-2-ones in excellent yields with excellent regioselectivity via a formal intramolecular arene C(sp2)-H amidation. The reactions of the 2- and 4-substituted aryl dioxazolones proceeds initially through spirolactamization via electrophilic amidation at the arene site, which is para or ortho to the substituent. A Hammett correlation study showed that the spirolactamization is likely to occur by electrophilic nitrenoid attack at the arene, which is characterized by a negative ρ value of -0.73.

Quantitative Analysis on Two-Point Ligand Modulation of Iridium Catalysts for Chemodivergent C-H Amidation

The transition-metal-catalyzed nitrenoid transfer reaction is one of the most attractive methods for installing a new C-N bond into diverse reactive units. While numerous selective aminations are known, understanding complex structural effects of the key intermediates on the observed chemoselectivity is still elusive in most cases. Herein, we report a designing approach to enable selective nitrenoid transfer leading to sp2 spirocyclization and sp3 C-H insertion by cooperative two-point modulation of ligands in the CpXIr(III)(κ2-chelate) catalyst system. Computational analysis led us to interrogate structural motifs that can be attributed to the desired mechanistic dichotomy. Multivariate linear regression analysis on the perturbation on the η5-cyclopentadienyl ancillary (CpX) and LX coligand, wherein we prepared over than 40 new catalysts for screening, allowed for construction of an intuitive yet robust statistical model that predicts a large set of chemoselective outcomes, implying that the catalysts' structural effects play a critical role on the chemoselective nitrenoid transfer. On the basis of this quantitative analysis, a new catalytic platform is now established for the unique lactam formation, leading to the unprecedented chemoselective reactivity (up to >20:1) toward a diverse array of competing sites, such as tertiary, secondary, benzylic, allylic C-H bonds, and aromatic πsystem.

A succinct synthesis of the vaulted biaryl ligand vanol via a dienone-phenol rearrangement

Vanol is a member of the vaulted biaryl family of ligands and it has been proven to be very effective in a number of asymmetric catalytic reactions. The previous synthesis of vanol, while effective, is limited by the cost of reagents involved. The present work evaluates three different approaches to the synthesis of 3-phenyl-1-naphthol, a key intermediate in the synthesis of vanol. The first approach has its key step as the Michael addition of a benzyl Grignard to methyl cinnamate. In the second approach the key step is the first step, a Reformatsky reaction of ethyl bromoacetate and deoxybenzoin. The final and most-efficient approach involves a dienone-phenol rearrangement of a 4-aryl-1-tetralenone generated in-situ from the reaction of 4-chloro-1-naphthol with AlCl3 and benzene, and preliminary results are reported on the extension of this method to substituted vanol derivatives.

Tetramethylethylene diamine/trimethylsilyl chloride mediated addition of benzyl copper reagents to α,β-unsaturated esters

Several benzylic copper reagents, benzylcopper, 4-methoxybenzylcopper and 1-phenylethylcopper, facilitate the conjugate addition of the corresponding benzyl ligands to α,β-enoates in the presence of tetramethylethylene diamine and trimethylsilyl chloride in high yields.

CONJUGATE ADDITION OF BENZYL COPPER REAGENTS TO α,β-ENOATES AND -ENONES.

Several benzylic copper reagents, BnCu(CN)MgCl, Bn2CuMgCl, BnCu-TMSCl-HMPA, and BnCu-TMSCl-TMEDA, facilitate the conjugate addition of the benzyl ligand to α,b-enones, but only BnCu-TMSCl-TMEDA gave high yields with α,β-unsaturated esters.