71040-85-2Relevant 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 (2007/10/03)
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.
Electrophilic claevage of cyclopropanes. IV. The reaction of 2-nitrobenzenesulphenyl chloride with tetracyclo2.7.04.6>heptane and acetic acid: the crystal structure of exo-3-(2'-nitrophenylthio)-exo-5-methoxytricyclo<2.2.1.0<
Garratt, Dennis G.,Przybylska, Maria,Cygler, Miroslaw
, p. 1176 - 1184 (2007/10/02)
The electrophilic cleavage of a cyclopropane single bond in tetracyclo2.7.04.6>heptane by 2-nitrobenzenesulphenyl chloride in methanol and acetic acid has been studied using both nmr and single crystal X-ray structural determ
Reaction of 2,4-Dinitrobenzenesulfenyl Chloride with Quadricyclene
Zefirov, Nikolai S.,Sadovaya, N. K.,Velikokhat'ko, T. N.,Andreeva, L. A.,Morrill, Terence C.
, p. 1468 - 1471 (2007/10/02)
The treatment of quadricyclene with 2,4-dinitrobenzenesulfenyl chloride has been reinvestigated and chloro adducts 1-A and 2b-A as well as acetates 4a-A, 4b-A, 6, and 7 have been obtained.Establishing 2b-A with endo-chloride led to important conclusion that endo-chloride attack occurs by collapse of ion pair.Monitoring changes in the proportions of acetates, especially with added LiClO4, has allowed conclusions about the degree of development of the carbocation intermediates.These conclusions were proposed on the basis of the previously published ideas of stereocontrol by an ion pair.
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.
Electrophilic cleavage of cyclopropanes. II. Concerning the effect of increasing electron demand upon the product-determining transition state in the reaction of 4-substituted-2-nitrobenzenesulphenyl chlorides and benzenesulphenyl chlorides with tetracyclo2,7.04,6>heptane....
Beaulieu, Pierre L.,Kabo, Ann,Garratt, Dennis G.
, p. 1014 - 1020 (2007/10/02)
The effect of increasing electron demand upon the product-determining transition state in the reaction of arenesulphenyl chlorides with tetracyclo2,7.04,6>heptane has been investigated.As the electron donating ability of the remote substituents on the phenyl ring of the sulphenyl chloride is varied from nitro to methoxy the relative proportion of adducts derived from edge-on attack is found to increase relative to that of adducts derived from corner attack.An ortho-nitro group was found to lead to a stabilizing interaction only in the case of 2,4-dinitrobenzenesulphenyl chloride.A mechanism involving the competition between the two conceptual modes of approach is suggested.
