71075-05-3Relevant academic research and scientific papers
Reaction of bicyclo[2.2.1]hepta-2,5-diene with the arenesulfenamide-phosphorus(v) oxohalide system: Chemo-, regio-, and steroselectivity
Zyk,Beloglazkina,Belova,Leshcheva,Zefirov
, p. 1468 - 1477 (2002)
The chemo-, regio- and stereoselectivities of electrophilic sulfenylation of bicyclo[2.2.1]hepta-2,5-diene with arenesulfenamides activated by phosphorus(v) oxohalides were studied. The ratio of the products of endo- to exo-attack of the diene by the electrophilic species depends on the solvent nature. The proportions of the products formed upon addition to one double bond and upon homoallylic participation of the second double bond depend on solvent polarity, the nature of the halogen, the substituents in the sulfenamide benzene ring, and on the reaction time. In addition, the formation of mixed adducts was proven for the reaction carried out in acetonitrile and the formation of disulfenylation products was found in the reaction with excess sulfenylating reagent. Isomerization of exo-3-arylthio-endo-2-halobicyclo[2.2.1]hept-5-enes to the products formed with homoallylic participation of the second double bond, exo-5-arylthio-endo-3-halotricyclo[2.2.1.02,6]heptanes, was shown to be possible.
REACTION OF ARENESULFENYL CHLORIDES WITH NORBORNADIENE
Zefirov, N. S.,Sadovaya, N. K.,Akhmedova, R. Sh.,Bodrikov, I. V.,Morrill, T. C.,et al.
, p. 503 - 510 (2007/10/02)
The reaction of o-nitro- and 2,4-dinitrobenzenesulfenyl chlorides with norbornadiene in carbon tetrachloride leads to the preferential formation of trans-2-endo-chloro-3-exo-(arylthio)norbornene with exo attack by the sulfenyl chloride.In acetic acid the main product is 5-(arylthio)-3-chloronortricyclene, which is obtained as a result of homoallylic participation of the second double bond; its structure and configuration were established by x-ray crystallographic analysis.In both cases the formation of trans-2-exo-chloro-3-endo-(arylthio)norbornene was also observed.Under "doping-addition" conditions (AcOH + LiClO4) the reaction occurs mainly with participation of the solvent in the concluding stage, and the products are the stereoisomeric nortricyclene acetoxy sulfides.The application of the previously proposed concept of stereochemical control of the configuration of the product in an ion-pair mechanism is discussed for the case of the investigated reactions.
