67615-59-2

Upstream product

• 74157-93-0 trans-1-phenyl-3-penten-1-one 
• 74175-88-5 (E)-2,2-dimethyl-1-phenylpent-3-en-1-one 
• 141-79-7 4-methyl-pent-3-en-2-one 
• 98-07-7 Benzotrichlorid 
• 20687-01-8 1-iodo-2-methylpropene 
• 93-55-0 1-phenyl-propan-1-one 
• 79910-78-4 (Z)-2,4-Dimethyl-1-phenyl-pent-2-en-1-one 
• 3017-69-4 2-methyl-1-propenylbromide 
• 513-37-1 2-methylprop-1-enyl chloride 
• 591-51-5 phenyllithium 
• 1617-32-9 (E)-3-pentenoic acid 
• 98-88-4 benzoyl chloride 

Relevant academic research and scientific papers

Reductive couplings of acid chlorides mediated by SmI2

Reductive couplings of acid chlorides and of acid chlorides with aldehydes or ketones in presence of an excess of SmI2 produce ketones in moderate to good yields.

Enantiodivergent Prenylation via Deconjugative Isomerization

Enantioselective platforms to facilitate prenylation are potentially expansive for translational research due to the importance of this motif as a key regulatory of biological function. Motivated by the conspicuous dearth of methods to generate chiral prenyl fragments for contemporary drug discovery, a light-enabled deconjugative isomerization of activated alkenes containing an aryl ketone antenna is disclosed through sequential geometric isomerization/hydrogen atom transfer (HAT)/protonation. Detailed mechanistic analyses have guided the development of an enantioselective variant of this atom economical process (up to 99% and 95:5 e.r.). Importantly, the chiral pool quasi-enantiomers quinine and quinidine serve as effective catalysts, thereby rendering this addition to the chiral drug discovery module portfolio enantiodivergent.

Ni-Catalyzed Alkenylation of Ketone Enolates under Mild Conditions: Catalyst Identification and Optimization

A procedure for Ni-catalyzed cross-coupling of ketone enolates with alkenyl halides has been developed. Intermolecular coupling of aromatic and aliphatic ketone lithium enolates with a variety of alkenyl halides is achieved in the presence of Ni(cod)2 catalyst (5 mol %), an N-heterocyclic carbene (NHC) ligand, and LiI (10 mol %) at 6-22 °C for 0.5-12 h with yields of up to 90%. During the initial development of this reaction, a misleading result with respect to the actual active catalyst was obtained using commercially available Q-Phos ligand, which was found to contain a trace of Pd metal contaminant sufficient to catalyze the reaction. However, under the final conditions optimized for Ni(cod)2 in the presence of an NHC ligand, Pd was incompetent as a catalyst.

Palladium-catalyzed alkenylation of ketone enolates under mild conditions

A protocol for a mild, catalytic, intermolecular alkenylation of ketone enolates has been developed using a Pd/Q-Phos catalyst. Efficient intermolecular coupling of a variety of ketones with alkenyl bromides was achieved with a slight excess of LiHMDS and temperatures down to 0 °C.

Cathodic Addition of Benzylidyne Trichloride to Ketones and Aldehydes

Ketones are converted to homologated enones 7a-g in good yields by cathodic addition of benzylidyne trichloride (1d).As intermediates α-Chlorooxiranes 6 are assumed, which rearrange via α-keto carbenium ions 9 to enones.The intermediacy of 9 is supported by the addition of 1d to norcamphor, where the products indicate equilibrating norbornyl cations as intermediates. α,β-Unsaturated ketones lead depending on steric shielding of the double bond to the cyclopropane 23 as 1,4-adduct or the enone 26 as 1,2-adduct.With aldehydes and 1d, α-chloro or βhydroxy ketones, the conversion products of 2-chlorooxiranes, are obtained.

Photochemistry of Acylic βγ-Unsaturated Ketones. Part 4. The Effect of α-Methyl Substitution with Some Hex-4-en-2-ones and 1-Phenylpent-3-en-1-ones

The photochemistry of the two hex-4-en-2-ones (1a and b), and the three 1-phenylpent-3-en-1-ones (1c-e) have been studied.Upon direct irradiation (1a) shows exclusively (E)-(Z) isomerization, whereas (1b) yields only α-cleavage products, illustrating competition between (E)-(Z) isomerization and α-cleavage for the hex-4-en-2-ones.Upon direct irradiation of (1c) no photochemical reaction is observed, but with (1d and e) products resulting from the α-cleavage reaction are obtained.Upon triplet sensitized irradiation (1a and b) yield the corresponding (Z)-isomers, but (1d) gives α-cleavage products.The difference in α-cleavage abili ty between (1a and c) on the one hand and (1b, d, and e) on the other upon direct irradiation is ascribed to the effect of α-methyl substitution.The difference in the photochemical behaviour of the hex-4-en-2-ones (1a and b) compared with that of the 1-phenylpent-3-en-1-ones (1c-e) is rationalized in terms of differences in the triplet state energy levels of the two types of βγ-enones.