Regiospecific addition of benzeneselenenyl halide to 1,1-dis ubstituted olefins

Abstract

The reaction of benzeneselenenyl halide with a variety of 1,1-disubstituted olefins under controlled conditions yields regiospecifically the anti-Markovnikov adducts which have been converted into the synthetically useful vinyl halides and allylhalides.

(+)-(1R,2S,3S,4S)-2-Chloro-3-(phenylselanyl)cyclohexane-1,4-diol

“…In the course of investigating other useful electrophilic additions, we attempted addition of phenylselenenyl chloride across the alkene of the bicyclic peroxide 2,3-dioxa-bicyclo[2.2.2]oct-7ene. Such additions have been well documented on other alkene bearing organic compounds (Engman, 1989;Toshimitsu et al, 1981Toshimitsu et al, , 1985, generally giving trans-1,2-phenylselenyl chloro adducts (Ho & Kolt, 1982;Clive et al, 1977), or in the presence of other nucleophiles, such as water or methanol, phenylselenenly alkoxide adducts can be formed (Nicolaou et al, 1979;Tiecco et al, 1988). Interestingly, addition of phenylselenenyl chloride to the peroxide was accompanied by simultaneous reduction of the peroxide bond to give the cyclohexyl-1,4-diol, (I).…”

“…For related literature, see: Clive et al (1977); Engman (1989); Greatrex et al (2003); Ho & Kolt (1982); Nicolaou et al (1979); Robinson et al (2006); Tiecco et al (1988); Toshimitsu et al (1981Toshimitsu et al ( , 1985.…”