75463-12-6

Upstream product

• 82994-41-0 β-tributylstannylpropionaldehyde 
• 3185-99-7 Methyl p-tolyl sulfone 
• 624-31-7 4-tolyl iodide 
• 7051-34-5 cyclopropylcarbinyl bromide 
• 98-59-9 p-toluenesulfonyl chloride 
• 5162-44-7 1-bromo-4-butene 

Downstream Products

• 71098-98-1 6-iodo-1-hexene 

Relevant academic research and scientific papers

Multicomponent Reductive Cross-Coupling of an Inorganic Sulfur Dioxide Surrogate: Straightforward Construction of Diversely Functionalized Sulfones

Conventionally, sulfones are prepared by oxidation of sulfides with strong oxidants. Now, a multicomponent reductive cross-coupling involving an inorganic salt (sodium metabisulfite) for the straightforward construction of sulfones is disclosed. Both intramolecular and intermolecular reductive cross-couplings were comprehensively explored, and diverse sulfones were accessible from the corresponding alkyl and aryl halides. Intramolecular cyclic sulfones were systematically obtained from five- to twelve-membered rings. Naturally occurring aliphatic systems, such as steroids, saccharides, and amino acids, were highly compatible with the SO2-insertion reductive cross-coupling. Four clinically applied drug molecules, which include multiple heteroatoms and functional groups with active hydrogens, were successfully prepared via a late-stage SO2 insertion. Mechanistic studies show that alkyl radicals and sulfonyl radicals were both involved as intermediates in this transformation.

Homolytic Displacement at Saturated Carbon: Part 5. Synthesis of Cyclopropylmethyl, Bicyclohex-2-yl, Bicyclohept-2-yl and Cyclohexanespirocycloprop-2-yl Sulphones from the Corresponding But-3-enylcobaloximes

But-3-enylcobaloxime reacts with arenesulphonyl chlorides under thermal and photochemical conditions to give cyclopropylmethyl sulphones.The yields depend upon the reaction conditions used.Similar reactions of cyclopent-2-enylmethylcobaloxime and cyclohex-2-enylmethylcobaloximes under photochemical conditions form a mixture of cis and trans isomers of bicyclohex-2-yl and bicyclohept-2-yl sulphones in (50:50) and (70:30) isomeric ratios respectively.However, cyclohex-3-enylcobaloximes form only the trans-bicyclohex-2-yl sulphone.Exclusive formation of cycloalkanespirocycloprop-2-yl sulphones is observed in the reactions of 2-(cyclo alk-1-enyl)ethylcobaloximes with arenesulphonyl chlorides.The reactions are free radical in nature and are believed to take place by a chain mechanism.In the key step a homolytic attack of the RSO2 radical at the terminal (δ) carbon of the butenyl ligand leads to the cyclized product.The exact nature of the ring closure step is uncertain, as both concerted and stepwise mechanisms are possible.

β-STANNYLPROPIONALDEHYDE. A VERSATILE CYCLOPROPANE BUILDING-BLOCK

Various functional group-substituted cyclopropanes were prepared in good yield starting from β-tributylstannylpropionaldehyde via homoallyl-stannanes or γ-hydroxypropylstannanes.

HOMOLYTIC DISPLACEMENT AT CARBON. V. FORMATION OF CYCLOPROPYLCARBINYLSULPHONES AND TRICHLOROETHYLCYCLOPROPANES FROM BUT-3-ENYL COBALOXIMES BY A NOVEL PROCESS INVOLVING HOMOLYTIC ATTACK AT THE δ-CARBON OF THE BUTENYL LIGAND

But-3-enyl- and substituted but-3-enylcobaloximes react with bromotrichlormethane (or trichloromethanesulphonyl chloride) and with 4-toluenesulphonyl chloride thermally or photochemically to give good yields of β,β,β-trichloroethylcyclopropanes and cyclopropylcarbinyl(tolyl)sulphones, respectively.The reactions proceed by a chain mechanism in which a key step is a novel process in which homolytic attack of a trichloromethyl or 4-toluenesulphonyl radical at the δ-carbon of the butenyl ligand leads to synchronous or subsequent attack of the incipient γ-carbon radical on the α-carbon, causing cyclisation and displacement of cobaloxime(II).The other propagation step involves the reaction of the cobaloxime(II) with the bromotrichloromethane, trichloromethanesulphonyl chloride or 4-toluenesulphonyl chloride to give the reactive organic radical.