89506-40-1

Upstream product

• 83-33-0 inden-1-one 
• 532-27-4 1-chloroacetophenone 
• 70-11-1 α-bromoacetophenone 
• 22955-77-7 methyl 1-indanone-2-carboxylate 
• 89506-31-0 Spirohept-5-en-2,2'-indan>-1'-on 
• 67153-85-9 2-dimethylaminomethyl-indan-1-one 
• 13261-70-6 2-methylidene-2,3-dihydro-1H-inden-1-one 
• 100-52-7 benzaldehyde 

Downstream Products

• 1325642-75-8 1-(2-ethoxyethyl)-2-phenyl-1,4-dihydroindeno[1,2-b]pyrrole 
• 1325642-79-2 1-cyclohexyl-2-phenyl-1,4-dihydroindeno[1,2-b]pyrrole 
• 1325642-78-1 1,2-diphenyl-1,4-dihydroindeno[1,2-b]pyrrole 
• 1325642-80-5 1-(methoxycarbonylmethyl)-2-phenyl-1,4-dihydroindeno[1,2-b]pyrrole 
• 1325642-72-5 1-benzyl-2-phenyl-1,4-dihydroindeno[1,2-b]pyrrole 

Relevant academic research and scientific papers

Mild Homologation of Esters through Continuous Flow Chloroacetate Claisen Reactions

The selective chloromethylenation of functionalized esters using chloroacetic acid (CA) and LiHMDS (HMDS=hexamethyldisilazide) in a continuous-flow setup is reported. This Claisen homologation is for the first time extended to bis-chloromethylenation using dichloroacetic acid (DCA), thus giving access to under-explored α,α′-bis-chloroketones. The use of flow conditions enables efficient generation and reaction of the unstable chloroacetate dianion intermediates, leading to unprecedented mild and scalable reaction conditions at an economical reagent stoichiometry (?10 °C, 1 min, 1.0–2.4 equiv dianion). The clean reaction profiles allow subsequent use of the unpurified crude products, which is demonstrated in the synthesis of various heterocycles of broad interest. Furthermore, we report a novel, catalyst-free substitution of the obtained monochloro ketone products with (hetero)aryl zinc enolates to give valuable 1,4-diketones.

Synthesis of benzo[c]azocanones and indeno[1,2-b]pyrroles from oxoindanecarboxylates

Ethyl 1-oxo-indane-2-carboxylate with a 1,4-diketone motif gave a benzo[c]azocane-1-one derivative-an eight-membered ring lactam-in a bismuth-mediated ring-expansion reaction with methylamine (40% yield). Yields with other primary amines were significantly lower. The ester function in the heterocyclic product could be saponified to give the free carboxylic acid, which was further amidated with para-bromoaniline. The molecular structure of the latter was established by X-ray single-crystal analysis. Benzo[c]azocanones exist in two diastereoisomeric conformations, causing double signal sets in the NMR spectra. Slow interconversion between these conformers was proved by EXSY NMR spectroscopy. Moreover, a conformational analysis by DFT calculations revealed the two diastereoisomers to be boat conformers that interconvert through a twist conformer. The maximum barrier for this process was calculated to be approximately 70 kJ/mol. Reaction of the corresponding methyl 1-oxoindane-2-carboxylate with methylamine gave the benzo[c]azocanone in lower yield. A spirolactam and an indeno[1,2-b]pyrrole were formed as further products. When using an indanone-derived 1,4-diketone without an ester function, several primary amines could be used in a bismuth-catalyzed Paal-Knorr reaction to give indeno[1,2-b]pyrrole derivatives with up to quantitative yields in several cases. Attempts to synthesize a caprolactam derivative from a cyclobutanone derived β-oxo ester with 1,4-diketone motif were unsuccessful.

Addition of Aldehydes to Activated Double Bonds, XXXIV. Addition of Aldehydes to Cyclic α-Methylene Ketones

The thiazolium salt-catalyzed addition of aldehydes to the cyclic α-methylene ketones 3, 4, 7, 8, 48, and 49 leads to γ-diketones 9 - 22, 50 - 53; some of them were converted into unsaturated ketones 23 - 28, pyrroles 29 - 34, 37 - 43, and furans 35, 36,