27326-83-6

Upstream product

• 39910-34-4 ethyl 2-diazo-2-(1-hydroxycyclobutyl)acetate 
• 71-43-2 benzene 
• 122539-74-6 2-trifluoromethanesulfonyloxy-cyclopent-1-enecarboxylic acid ethyl ester 
• 98-80-6 phenylboronic acid 
• 611-10-9 2-ethoxycarbonyl-1-cyclopentanone 
• 94-02-0 ethyl 3-oxo-3-phenylpropionate 
• 4535-59-5 ethyl 2-benzoyl-5-methylhex-4-enoate 
• 108-86-1 bromobenzene 
• 42593-09-9 Ethyl 2-acetoxy-1-cyclopentene-1-carboxylate 

Downstream Products

• 156774-71-9 2-phenyl-cyclopent-1-enecarboxylic acid 

Relevant academic research and scientific papers

Exploring the Limits of π-Acid Catalysis Using Strongly Electrophilic Main Group Metal Complexes: The Case of Zinc and Aluminium

The catalytic activity of cationic NHC-ZnII and NHC-AlIII (NHC=N-heterocyclic carbene) complexes in reactions that require the electrophilic activation of soft C?C π bonds has been studied. The former proved able to act as a soft π-L

Lewis Superacidic Catecholato Phosphonium Ions: Phosphorus-Ligand Cooperative C-H Bond Activation

A series of catecholato phosphonium ions, including the first stable bis(catecholato)-substituted derivatives, are isolated and fully characterized. The cations rank among the most potent literature-known Lewis acids on the Gutmann-Beckett and ion affinit

Carbonyl-Olefin Metathesis Catalyzed by Molecular Iodine

The carbonyl-olefin metathesis reaction could facilitate rapid functional group interconversion and allow construction of complicated organic structures. Herein, we demonstrate that elemental iodine, a very simple catalyst, can efficiently promote this chemical transformation under mild reaction conditions. Our mechanistic studies revealed intriguing aspects of the activation mode via molecular iodine and the iodonium ion that could change the previously established perception of catalyst and substrate design for the carbonyl-olefin metathesis reaction.

Br?nsted Acid-Catalyzed Carbonyl-Olefin Metathesis inside a Self-Assembled Supramolecular Host

Carbonyl–olefin metathesis represents a powerful yet underdeveloped method for the formation of carbon–carbon bonds. So far, no Br?nsted acid based method for the catalytic carbonyl–olefin metathesis has been described. Herein, a cocatalytic system based on a simple Br?nsted acid (HCl) and a self-assembled supramolecular host is presented. The developed system compares well with the current benchmark catalyst for carbonyl–olefin metathesis in terms of substrate scope and yield of isolated product. Control experiments provide strong evidence that the reaction proceeds inside the cavity of the supramolecular host. A mechanistic probe indicates that a stepwise reaction mechanism is likely.

Cobalt-Catalyzed Cross-Couplings between Alkenyl Acetates and Aryl or Alkenyl Zinc Pivalates

CoBr2 (5 mol %) in the presence of 2,2′-bipyridyl (5 mol %) enables electrophilic alkenylations between easily accessible alkenyl acetates or tosylates and various functionalized aryl zinc pivalates at ambient temperature. This cobalt-catalyzed

Rhodium-catalyzed and zinc(II)-triflate-promoted asymmetric hydrogenation of tetrasubstituted α,β-unsaturated ketones

The asymmetric hydrogenation of tetrasubstituted α,β-unsaturated ketones has been accomplished using an in situ formed rhodium-Josiphos catalyst. The reaction is enhanced by addition of catalytic zinc(II) triflate, which significantly improves turnover fr

Palladium complex-catalyzed cross-coupling reaction of organobismuth dialkoxides with triflates

(matrix presented) Pd(PPh3)4 catalyzes cross-coupling reaction between organobismuth alkoxides and aryl and vinyl triflates.

The reaction of α-diazo-β-hydroxy esters with boron trifluoride etherate: Generation and rearrangement of destabilized vinyl cations. A detailed experimental and theoretical study

Cyclic ethyl 2-diazo-3-hydroxy carboxylates were prepared by treating ethyl diazoacetate with LDA followed by reaction with a series of cyclic ketones. Further treatment of these α-diazo-β-hydroxy esters with boron trifluoride etherate in various solvents affords an unusual array of products. Product types and ratios were found to be strongly dependent on ring size and the solvent used. The reaction proceeds by Lewis acid complexation of the alcohol functionality of the diazo hydroxy ester with BF3 etherate followed by neighboring-group participation of the diazo moiety to generate a cycloalkylidene diazonium salt. Loss of nitrogen produces a highly reactive, destabilized, linear vinyl cation. Ring expansion via a 1,2-methylene shift leads to the formation of a more stable, bent cycloalkenyl vinyl cation. A subsequent 1,2-methylene shift results in ring contraction ultimately leading to a stable allylic cation. This cation is either trapped by the solvent or else undergoes cyclization with the adjacent ester group to give a lactone. Computational studies at the 6-31G* level were performed to determine the geometry of the optimized vinyl cations. Relative energies suggest a moderate energy gain for isomerization of the initial vinyl cation V1 to the rearranged vinyl cation V2 followed by a large stabilization in energy for subsequent conversion to the allyl cation A1. Compared with isolated product distributions, the energy profiles suggest kinetically-controlled V1 → V2 → A1 migrations. Finally, the calculations suggest that in diethyl ether the carbocations may be coordinated to a molecule of solvent resulting in "protected" cationic intermediates with nonlinear geometries.