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The synthesis and reactivity of secondary and tertiary alkylzinc bromides and a new highly reactive form of Rieke zinc
Abstract
Secondary and tertiary alkylzinc bromides can be generated from the direct oxidative addition of Rieke zinc to secondary and tertiary alkyl bromides in high yield. These organozinc reagents have been found to undergo copper-catalyzed conjugate addition, cross-coupling with acid chlorides, and carbocupration to activated alkynes. Secondary and tertiary alkylzinc bromides can react in a 1,4-addition mode directly to $\alpha,\beta$-unsaturated ketones in the presence of Lewis acids without the need for a copper catalyst. The reduction of zinc cyanide by lithium naphthalenide yields an active form of zinc which undergoes oxidative addition to alkylchlorides with the tolerance of some functionality. Reaction of dihalobenzenes and 2,5-dibromothiophene with Rieke magnesium, Rieke zinc, and Rieke calcium at low temperature affords a mono-organometallic intermediate which upon subsequent treatment with an electrophile provides a mono-functionalized aromatic product in excellent chemical yield. The direct formation of organomanganese bromides can be accomplished under mild conditions from the direct oxidative addition of Rieke manganese to alkyl and thienyl bromides.
Subject Area
Organic chemistry
Recommended Citation
Hanson, Mark Vincent, "The synthesis and reactivity of secondary and tertiary alkylzinc bromides and a new highly reactive form of Rieke zinc" (1996). ETD collection for University of Nebraska-Lincoln. AAI9637070.
https://digitalcommons.unl.edu/dissertations/AAI9637070