94083-38-2

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• 103-25-3 3-phenylpropanoic acid methyl ester 
• 51348-74-4 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropane-1-carbonyl chloride 

Relevant academic research and scientific papers

Efficient α-chlorination of carbonyl containing compounds under basic conditions using methyl chlorosulfate

An efficient method for the α-chlorination of ketones under basic conditions is described using methyl chlorosulfate. Its applicability for the chlorination of other functional groups has also been studied and it is equally useful for the synthesis of α-chloroesters and amides. Methyl chlorosulfate is described for the first time as a positive chlorine source. Some aldol reactions which occur during the chlorination of some substrates are also reported.

Unexpected Direct Synthesis of N-Vinyl Amides through Vinyl Azide–Enolate [3+2] Cycloaddition

The unexpected synthesis of industrially important N-vinyl amides directly from aldehydes and α,β-unsaturated N-vinyl amides from esters is reported. This reaction probably proceeds through an initial [3+2] azide–enolate cycloaddition involving a vinyl azide generated in situ. A survey of the reaction scope and preliminary mechanistic findings supported by quantum computational analysis are reported, with implications for the future development of atom-efficient amide synthesis. Intriguingly, this study suggests that (cautious) reevaluation of azidoethene as a synthetic reagent may be warranted.

Ti-Crossed-Claisen condensation between carboxylic esters and acid chlorides or acids: A highly selective and general method for the preparation of various β-keto esters

Ti-crossed-Claisen condensation between a 1:1 mixture of carboxylic esters and acid chlorides promoted by TiCl4-Bu3N-N-methylimidazole proceeded successfully to give various β-keto esters in good yields with excellent selectivities (19 examples, ～48-95% yield; cross/self-selectivity = ～96/4-99/1). The present method was extended to the condensation between a 1:1 mixture of carboxylic acids and carboxylic esters (six examples, ～70-92% yield; cross/self-selectivity = ～91/9-99/1). To demonstrate the utility of the present two Ti-crossed-Claisen condensations, we performed a couple of efficient short-step syntheses of two natural, representative, and useful perfumes, cis-jasmone and (R)-muscone. Copyright

TiCl4/Bu3N/(catalytic TMSOTf): Efficient agent for direct aldol addition and claisen condensation

TiCl4/Bu3N conducts highly efficient cross aldol additions between different ketones and between ketones and aldehydes, in good to excellent yields with high syn-stereoselectivities. As an extension, direct Claisen condensation between methyl esters was also promoted by TiCl4/Bu3N with 0.05 equiv of TMSOTf co-catalyst.

THE SELECTIVE CLAISEN AND DIECKMANN ESTER CONDENSATION PROMOTED BY DICHLOROBIS(TRIFLUOROMETHANESULFONATO)TITANIUM(IV)

Inter and intramolecular condensations (the Claisen and the Dieckmann condensations) between ester functions have been performed by the combined use of dichlorobis(trifluoromethanesulfonato)titanium(IV) (=dichlorobis(triflato)titanium(IV)) and tertiary amine under mild reaction conditions.These results led to the development of the selective (crossed) Claisen and Dieckmann ester condensation between methoxymethyl ester and methyl ester, in that, dichlorobis(triflato)titanum(IV) contribute to control the direction of the reaction.

DICHLORO-BIS(TRIFLUOROMETHANESULFONATO)TITANIUM(IV) AS AN EFFECTIVE PROMOTER IN THE CLAISEN ESTER CONDENSATION

Inter- and intra-molecular condensation (the Claisen and the Dieckmann condensations) between ester functions have been effected by the combined use of dichloro-bis(trifluoromethanesulfonato)titanium(IV) and tertiary amine under mild conditions.