Dihalocarbene reactions with steroid olefins Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/v118rh37p

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  • Dihalocarbenes have been generated mainly by thermal decomposition of sodium trihaloacetate and phenyl (trihalomethyl)mercury, and give gem-dihalocyclopropyl adducts with various steroid olefins. A new procedure involving the use of sealed tubes makes possible the addition of dihalocarbenes to sterically hindered olefins. In this manner, 7-cholestenyl benzoate when treated with PhHgCC1₃ furnished a 50% yield of the 7α, 8α adduct. Under forcing conditions cholesteryl benzoate was found to undergo an insertion reaction with dichloro- and dibromocarbene to produce 7α-dihalomethyl-5-cholesteryl benzoate. This represents a stereospecific dihalocarbene reaction. Dichlorocarbene was found to add, however, to isolated 5, 6 olefins of increased nucleophilicity such as 6-methylcholesteryl acetate. The stereochemistry of the various dihalocyclopropyl adducts has been demonstrated by correlation with compounds of known configuration prepared via stereospecific Simmons -Smith reactions. Both 5α, 6α and 5β, 6β cyclopropyl analogs of cholesterol have been prepared along with other small, strained ring steroids.
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