65288-16-6

Upstream product

• 65288-12-2 toluene-4-sulfonic acid 3-benzenesulfonyl-1-methylpropyl ester 
• 100-52-7 benzaldehyde 
• 78505-03-0 2-methyl-3-chloropropyl phenyl sulfone 
• 108-98-5 thiophenol 
• 64-17-5 ethanol 
• 3112-85-4 methylphenylsulfonate 
• 75-56-9 methyloxirane 
• 27998-52-3 (+/-)-4-(phenylthio)-2-butanol 
• 72444-56-5 Toluene-4-sulfonic acid 1-methyl-3-phenylsulfanyl-propyl ester 
• 104-87-0 4-methyl-benzaldehyde 
• 104-88-1 4-chlorobenzaldehyde 
• 123-11-5 4-methoxy-benzaldehyde 
• 123-72-8 butyraldehyde 
• 94-41-7 benzalacetophenone 

Relevant academic research and scientific papers

Stereospecific Synthesis of Enantioenriched Alkylidenecyclobutanones via Formal Vinylidene Insertion into Cyclopropanone Equivalents

1-Sulfonylcyclopropanols are employed here as efficient cyclopropanone equivalents in a formal vinylidene insertion process, providing the first general synthetic route to enantioenriched alkylidenecyclobutanones. The addition of an alkenyl-Grignard reage

CYCLOPROPANATION METHOD

A cyclopropanation method includes reacting an alcohol, an ester, or an aldehyde with a sulfone in an organic solvent containing a base providing a counter cation to form a cyclopropane; and isolating the cyclopropane.　When using the alcohol or ester, the organic solvent further contains a catalyst having an alcohol dehydrogenation activity.

Three-Component [1 + 1 + 1] Cyclopropanation with Ruthenium(II)

We report a one-step, Ru(II)-catalyzed cyclopropanation reaction that is conceptually different from the previously reported protocols that include Corey-Chaykovsky, Simmons-Smith, and metal-catalyzed carbene attack on olefins. Under the current protocol, various alcohols and esters are transformed into sulfone substituted cyclopropanes with excellent isolated yields and diastereoselectivities. This new reaction forms highly congested cyclopropane products with three new C-C bonds, three or two new chiral centers and one new quaternary carbon center. Twenty-two examples of isolated substrates are given. Previously reported synthetic routes for similar substrates are all multistep, linear routes that proceed with overall low yields and poor control of stereochemistry. Commercially available Ru(II) dehydrogenation catalysts, that were recently developed for the dehydrogenative synthesis of esters and amides from alcohol and amine substrates, were used in the reaction, with the best catalyst showing excellent activity at 0.2-1 mol % catalyst loading. Mechanistic investigation showed that in the case of alcohol substrates, the catalyst is only responsible for the first dehydrogenation step, and that the identity of the base and the countercation is crucial in achieving high yields. The catalyst is also required for the cyclopropanation of esters, although no dehydrogenation can proceed in this case, suggesting that substrates sensitive to H2 may be acylated prior to reaction.

Synthesis of substituted tetrahydrofurans via intermolecular reactions of γ-chlorocarbanions of 3-substituted 3-chloro-propylphenyl sulfones with aldehydes

Carbanions of 3-substituted-3-chloropropyl phenyl sulfones add to carbonyl groups of aldehydes to produce aldol type adducts that undergo 1,5-intramolecular substitution giving 2,3,5-trisubstituted tetrahydrofurans. The effect of substituents in the 3-pos

New reactions of γ-halocarbanions: Underestimated reactive intermediates in organic synthesis

Short-lived γ-halocarbanions can be trapped by active electrophiles such as aldehydes, imines, and Michael acceptors to give anionic adducts, which undergo intramolecular substitution to give substituted tetrahydrofurans, pyrrolidines, and cyclopentanes. This has underlain a new method for the synthesis of these valuable ring systems. We have determined the acidity of the γ-halocarbanion precursors and have shown that the halogen atoms in the γ-position relative to the carbanion center exert a significant stabilizing effect on the carbanion.

Acylations and aldol-type reactions of cyclopropyl α-sulfonyl carbanions

Acylations and aldol-type reactions of cyclopropyl α-sulfonyl carbanions formed from (1R*,2R*)-2-alkyl- 1-(phenylsulfonyl)cyclopropanes (1R*,2R*)- gave (1R*,2R*)-1-acyl-, and (1R*,2R*)-1-(1-hydroxyalkyl)-2- alkyl-1-(phenylsulfonyl)cyclopropanes [(1R*,2R*)

Applications of highly enantioenriched alcohols bearing a phenylthio group in the preparation of ring compounds. The two-pot synthesis of an enantiopure spiroacetal pheromone bearing three chiral centers

The new chiron (S)-6-phenylthio-2-hexanol (3) was prepared in high enantiomeric excess by baker's yeast reduction of the corresponding ketone. Enantioenriched alcohols 1, 2 and 3, prepared previously by a similar procedure, or their racemic counterparts, were transformed into ring closed compounds 5-methyl-2-(phenylthio)tetrahydrofuran (9), 6-methyl-2- (phenylthio)tetrahydropyran (10), 2-methyl-1-phenylsulfonyl cyclopropane (14), cyclobutane (15), cyclopentane (16), and a bee pheromone, (2S,6R,8S)- 2,8-dimethyl-1,7-dioxaspiro[5.5]undecane (20).