123700-03-8

Upstream product

• 5204-64-8 3-pentenoic acid 
• 79-37-8 oxalyl dichloride 
• 1617-32-9 (E)-3-pentenoic acid 
• 626-99-3 1,3-butadiene-1-carboxylic acid 
• 16529-66-1 3-Pentenenitrile 

Downstream Products

• 169691-41-2 (E)-Pent-3-enoic acid trityl-amide 
• 54716-19-7 (E)-N-phenylpent-3-enamide 
• 185670-22-8 (Z)-2-Methyl-3-((E)-pent-3-enoyl)-but-2-enedioic acid dibenzyl ester 
• 108-28-1 protoanemonin 
• 142422-31-9 cis-5,6-Dihydro-1,5-dimethyl-6-phenyl-2(1H)-pyridinone 
• 142541-19-3 (R,R;S,S)-1-Methyl-2-(hydroxybenzyl)-3-pentenamide 

Relevant academic research and scientific papers

Synthetic studies toward the total synthesis of tautomycetin

The studies culminating in the synthesis of two large subunits of tautomycetin are described. The first one, fragment C1-C12 that has an anti-1,3-dimethyl system and a terminal diene unit, was accomplished in 10 linear steps in 7.4% overall yield. The second one, fragment C13-C25 which bears the sensitive anhydride framework and the majority of the stereogenic centers, was prepared in 13 linear steps (longest sequence) in 8% overall yield. Among the key transformations used, a regioselective epoxide opening, a Pd-catalyzed addition of terminal alkyne to acceptor alkyne, a Mukaiyama aldol reaction, a Yamaguchi esterification, and a homemade mild di-esterification can be cited. The chosen strategies allowed good yields, stereoselectivity, reproducibility, and scalability for several important intermediates.

Dirhodium(II)-Mediated Alkene Epoxidation with Iodine(III) Oxidants

Dirhodium(II) complexes and iodine(III) oxidants have found useful applications in synthetic nitrene chemistry. In this study, the combination of the dirhodium(II) complex Rh2(tpa)4 (tpa = triphenylacetate) with the iodine(III) oxidant PhI(OPiv)2 is shown to promote the epoxidation of alkenes in the presence of 2 equivalents of water. The reaction can be applied to diversely substituted alkenes and the corresponding epoxides are isolated with yields of up to 90 %. A possible mechanism involves the dirhodium(II) complex as a Lewis acid species that would tune the oxidizing character of the iodine(III) reagent.

PROCESS TO PREPARE EPSILON-CAPROLACTAM

The invention is directed to a process to prepare ε-caprolactam and/or unsaturated ε-caprolactam from a pentenamide by contacting the pentenamide with a mixture of hydrogen and carbon monoxide in the presence of a solvent and a catalyst system comprising of a Group 8-10 metal and a phosphorus-donor ligand. The ligand may be a xantphos-type ligand.

Synthesis of γ-hydroxy α,β-unsaturated amides by base induced isomerization of epoxy amides

Treatment of 3,4-epoxyamides with LDA affords γ-hydroxy-α,β- unsaturated amides, usually with high (E)-selectivity. The 3,4-epoxyamides were prepared by the epoxidation of β,γ-unsaturated amides with meta- chloroperbenzoic acid.

Preparation of 3-pentenoic acid and a catalyst therefore

Preparation of 3-pentenoic acid by the reaction of 3-pentenoylchloride, water and butadiene. 3-chloro-1-butene and 1-chloro-2-butene are also formed. Preferably the 3-pentenoylchloride is formed by the reaction of chlorobutene with carbon monoxide using a palladium catalyst.

INTRAMOLECULAR DIELS-ALDER CYCLOADDITIONS OF VINYLKETENIMINES. A CONVERGENT ROUTE TO CARBAZOLES AND PYRIDOCARBAZOLE ALKALOIDS

The intramolecular Diels-Alder cycloaddition of acetylenic vinylketenimines is the key step of a highly convergent synthesis of carbazoles.A facile synthesis of N-methyl-tetrahydroellipticine has been completed in five isolated steps from N-methyl piperidone.