62999-73-9

Upstream product

• 505-23-7 1,3 dithiane 
• 122-52-1 triethyl phosphite 
• 183791-52-8 C₈H₁₆LiO₃PS₂ 
• 814-49-3 diethyl chlorophosphate 
• 57529-04-1 2-chloro-1,3-dithiane 

Downstream Products

• 145547-43-9 2-(2-benzylidenebutylene)-1,3-dithiane 
• 83268-77-3 6-phenyl-2,2-(trimethylenedithio)tetrahydropyran 
• 103563-41-3 (E)-(3S,4S,5S)-8-Benzyloxymethoxy-1-[1,3]dithian-2-ylidene-3,5-dimethyl-oct-6-en-4-ol 
• 103563-39-9 (Z)-(3S,4S,5R)-8-Benzyloxymethoxy-1-[1,3]dithian-2-ylidene-3,5-dimethyl-6-trimethylsilanyl-oct-6-en-4-ol 
• 83268-74-0 (E)-(3R,5R)-5-(tert-Butyl-dimethyl-silanyloxy)-1-(2,4-dichloro-phenyl)-7-[1,3]dithian-2-ylidene-hept-1-en-3-ol 
• 145547-46-2 2-(1,3-diphenyl-2-propenylidene)-1,3-dithiane 
• 145547-32-6 diethyl 1,1-(1,3-propylenedithio)-2,4-diphenyl-4-oxo-3-butanephosphonate 
• 17590-61-3 2-(3-phenyl-2-propenylidene)-1,3-dithiane 
• 145547-47-3 2-(1-methyl-3-phenyl-2-propenylidene)-1,3-dithiane 
• 145547-33-7 diethyl 1,1-(1,3-propylenedithio)-2-phenyl-4-oxo-pentanephosphonate 
• 1523-68-8 diethyl (1-oxopropyl)phosphonate 
• 13504-37-5 diethyl phenylacetylphosphonate 
• 1107648-79-2 2-[(S)-3-(1-methyl-1-nitroethyl)cyclohexylidene]-[1,3]dithiane 
• 1226497-30-8 2-((3R,4R)-4-(benzyloxymethoxy)-5-methyl-3-vinylhexylidene)-1,3-dithiane 

Relevant academic research and scientific papers

A new synthesis of α-ketophosphonates

α-Ketophosphonates are prepared from 2-alkyl-2-phosphonyl-1,3-dithianes.

The use of enantiomerically pure ketene dithioacetal bis(sulfoxides) in highly diastereoselective intramolecular nitrone cycloadditions. Application in the total synthesis of the beta-amino acid (-)-cispentacin and the first asymmetric synthesis of cis-(3R,4R)-4-amino-pyrrolidine-3-carboxylic acid.

Intramolecular 1,3-dipolar nitrone cycloaddition onto an enantiomerically pure ketene dithioacetal dioxide using a three-carbon tether gave the corresponding 5,5-disubstituted isoxazolidine as a single diastereomer in good yield. This reaction has been used as the key step in an asymmetric synthesis of the naturally occurring antibiotic, (-)-cispentacin. An asymmetric synthesis of 4-amino-pyrrolidine-3-carboxylic acid has also been carried out using the intramolecular nitrone cycloaddition as the stereocontrolling step.

Highly Diastereoselective Nitrone Cycloaddition onto a Chiral Ketene Equivalent: Asymmetric Synthesis of Cispentacin

matrix presented A highly diastereoselective intramolecular nitrone cycloaddition onto a chiral ketene equivalent, obtained by Horner-Wadsworth-Emmons olefination of either enantiomer of bis-sulfinyl phosphonate 6, is described. Cycloaddition gave 5,5-disubstituted isoxazolidine 10 in good yield as a single diastereomer. Catalytic hydrogenolysis of 10 furnished either enantiomer of optically pure cis-2-aminocyclopentane-1-carboxylic acid.

Oxidative cyclization based on reversing the polarity of enol ethers and ketene dithioacetals. Construction of a tetrahydrofuran ring and application to the synthesis of (+)-nemorensic acid

The utility of oxidative cyclization reactions for the construction of tetrahydrofuran rings has been examined. In these experiments, alcohol nucleophiles were found to be effective traps for radical cation intermediates generated from both enol ether and ketene dithioacetal groups, The reactivity of the alcohol trapping group appeared to lie between that of an enol ether and an allylsilane trapping group. The stereochemical outcome of cyclization reactions originating from the oxidation of an enol ether was found to be controlled by stereoelectronic factors. The utility of these cyclization reactions was illustrated with the synthesis of a key tetrahydrofuran building block for the synthesis of linalool oxide and rotundisine. Cyclization reactions triggered by the oxidation of a ketene dithioacetal led to far greater levels of stereoselectivity. The stereochemical outcome of these reactions was shown to arise from steric factors involving the larger ketene acetal group. The synthetic utility of cyclizations utilizing ketene dithioacetal derived radical cations was demonstrated by completing an asymmetric synthesis of (+)-nemorensic acid. Finally, the reactions were shown to be compatible with the use of an amide nucleophile and the direct formation of a lactone product.

Carbanionic displacement reactions at phosphorus: Synthesis and reactivity of 5,5-dimethyl-2-oxo-2-(1,3-dithian-2-yl)-1,3,2-dioxaphosphorinane

We describe the formation and reactivity of the lithiated carbanion of 5,5-dimethyl-2-oxo-2-(1,3-dithian-2-yl)-1,3,2-dioxaphosphorinane 3b.The derived carbanion 2b is prepared in quantitative yield by internal quench condensation of 1,3-dithiane and 2-chl

Stereoselective epoxidation of bis-sulfinyl alkenes and application to the asymmetric synthesis of α-substituted carboxylic acids

Ketene thioacetals 3 can be easily prepared in optically pure form and react diastereoselectively with metal peroxides. The resulting bis-sulfinyl oxiranes can be converted in a single step to α-substituted acids.