16192-04-4Relevant articles and documents
SO2 conversion to sulfones: Development and mechanistic insights of a sulfonylative Hiyama cross-coupling
Adenot, Aurélien,Char, Jo?lle,Von Wolff, Niklas,Lefèvre, Guillaume,Anthore-Dalion, Lucile,Cantat, Thibault
, p. 12924 - 12927 (2019)
A Pd-catalyzed Hiyama cross-coupling reaction using SO2 is described. The use of silicon-based nucleophiles leads to the formation of allyl sulfones under mild conditions with a broad functional group tolerance. Control experiments coupled with DFT calculations shed light on the key steps of the reaction mechanism, revealing the crucial role of a transient sulfinate anion.
Coupling reaction of magnesium alkylidene carbenoids with α-sulfonylallyllithiums: An efficient route to multi-substituted vinylallenes
Kimura, Tsutomu,Kobayashi, Gen,Ishigaki, Masashi,Inumaru, Mio,Sakurada, Jo,Satoh, Tsuyoshi
, p. 3623 - 3632 (2013/02/23)
A variety of vinylallenes were successfully synthesized from 1-chlorovinyl p-tolyl sulfoxides and allyl or vinyl sulfones. Allyl and vinyl sulfones served as α-sulfonylallyllithium sources were prepared from carbonyl compounds in three or four steps in good overall yields. The coupling reaction of α-sulfonylallyllithiums with magnesium alkylidene carbenoids, which were generated from 1-chlorovinyl p-tolyl sulfoxides and isopropylmagnesium chloride, afforded multi-substituted vinylallenes in up to 88% yield. Georg Thieme Verlag KG Stuttgart · New York.
Radical-chain reactions of sulfonyl azides and of ethyl azidoformate with allylstannanes: Homolytic allylation at nitrogen
Dang, Hai-Shan,Roberts, Brian P.
, p. 1493 - 1498 (2007/10/03)
4-Methylbenzenesulfonyl azide reacts with allyltriphenylstannane (ATPS) in refluxing benzene, in the presence of 2,2′-azobis(2-methylpropionitrile) as initiator, to give N-allyl-4-methylbenzenesulfonamide in good yield after hydrolytic work-up. Small amounts of allyl 4-methylphenyl sulfone were also formed. The reaction follows a free-radical chain mechanism which involves competitive addition of Ph5Sn? to Na and to Nc of the azido group in ArSO2NaNbNc. Addition to Na followed by loss of nitrogen gives ArSO2NSnPh3, the precursor of the N-allylarenesulfonamide, while addition to Nc leads to the formation of ArSO2 and thence to the allyl aryl sulfone. Allyltrimethylstannane behaves in a similar way to ATPS, but allyltributylstannane gives only a low yield of N-allylarenesulfonamide and the major product is the unsubstituted sulfonamide MeC6H4SO2NH2, which results because the radical ArSO2NSnBu3 undergoes intramolecular 1,5-hydrogen-atom transfer in preference to adding to the allylstannane. 2-Methylallyltriphenylstannane reacts in an analogous way to ATPS, but allylstannanes containing non-terminal double bonds do not react successfully. The arenesulfonyl azides 4-XC6H4SO2N3 (X = H, MeO, F) react in a similar way to tosyl azide, but the reaction is very sluggish when X = NO2? With 1-octanesulfonyl azide, reaction with Ph3Sn? is much less selective and products arising from attack at Na and Nc are formed in comparable yields. Ethyl azidoformate reacts with allylstannanes in a similar manner to, although more slowly than, tosyl azide and gives good yields of the corresponding allylic carbamates.
