The existence of dioxacarbenes have been reported, but have not yet realized any synthetic utility. A dioxacarbene has been suggested as an intermediate in the Corey-Winter olefination reaction where a thiocarbonate is reacted with trimethyl phosphite. Since thiocarbonates and carbonates are readily accessible from the corresponding diols, it would seem this represents a useful route to access a dioxacarbene. We envisioned that the dioxacarbene could be reacted with an olefin to afford a cyclopropanone acetal. This cyclopropanone acetal could be synthetically useful as it could be readily incorporated in to larger molecules. Provided that the dioxacarbene could react with a variety of olefins then this new methodology could be utilized in a diversity oriented synthesis approach. To realize this ultimate goal, we have synthesized a variety of carbonates and thiocarbonates. These carbonates and thiocarbonates have been reacted with several different olefins in the presence of trimethyl phosphite under a variety of conditions. Although a cyclopropanone acetal has not yet been isolated, important information has been discerned about the nature of any potential dioxacarbene and whether or not it is truly an intermediate in the reaction of a thiocarbonate with trimethyl phosphite.

Generating dioxacarbenes from carbonates and thiocarbonates and the implications for the mechanism of the Corey-Winter olefination

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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