75805-63-9Relevant academic research and scientific papers
Electrophilic additions to allenes. VII. The role of steric versus electronic effects in the reactions of areneselenenyl halides with allenes
Garratt, Dennis G.,Beaulieu, Pierre L.,Morisset, Veronique M.,Ujjainwalla, Mark
, p. 2745 - 2753 (2007/10/02)
The reactions of benzeneselenenyl chloride, bromide, and 2,4,6-trimethylbenzeneselenenyl bromide with alkyl 1,3-disubstituted allenes in methylene chloride solution have been investigated.While kinetic data are in accord with similar rate determining transition states, exhibiting strong steric effects for all three species, the product distributions show changes in both chemoselectivity and configurational-selectivity in accord with two different types of steric interaction mechanisms during the product determining transition states.A mechanism involving rate limiting formation of alkylideneseleniranium ions and/or alkylideneepiselenuranes, followed by isomerization between the alkylideneseleniranium ions by a path not involving allylic ions, prior to the product determining transition states, is proposed.
ELECTROPHILIC ADDITIONS TO ALLENES-II; THE REACTION OF BENZENESELENENYL CHLORIDE WITH SOME 1,3-DISUBSTITUTED ALLENES
Garratt, Dennis G.,Beaulieu, Pierre L.,Ryan, M. Dominic
, p. 1507 - 1514 (2007/10/02)
Benzeneselenenyl chloride reacts with 1,3-dialkyl-substituted allenes in methylene chloride solution to give 1:1-adducts.Attack by selenium is found to occur exclusively at the central allenic carbon.In contrast to the analogous reaction of arenesulphenyl chlorides, the preferential formation of the Z-alkene is observed.A mechanism involving the preequilibrium formation of alkylideneseleniranium ions and/or alkylideneepiselenuranes which, in the product-determining step, collapse to products via an anti attack of chloride at the methine carbon of the ring is proposed to account for the preferential formation of the Z-isomers.
