High levels of diastereoselectivity have been observed for Grignard reactions of macrocyclic 1,4-diketones. In all of the macrocycles investigated, ring size proved to be the greatest contributor to diastereoselectivity. As the size of the macrocyclic (1,4-diketone) system employed decreases, the observed diastereoselectivity of the 1,2-addition increases. These results led to an investigation of enolate alkylations on the same macrocyclic 1,4-diketones as a means to alkylate the α and α' positions diastereoselectively. Similarly, high levels of diastereoselectivity where obtained in these vicinal alkylation reactions. The resulting macrocyclic 1,4-diketones were subsequently subjected to a five step sequence, featuring a transannular McMurry reaction, to afford the all trans relative stereochemistry of several lignan-type natural products.

Diastereoselective transformations of macrocyclic 1,4-diketones and their application to the total synthesis of cyclobutane-containing natural products

Macromolecular Chemistry: The Second Century

[Author Benefits](https://scimeetings.acs.org/?utm_source=pubs_content_marketing&utm_medium=website&utm_campaign=0320_MCF_NPI_Launch_Spring_Homepage&ref=pubs_content_marketing)

[How to use SciMeetings](https://storage.googleapis.com/dl.morressier.com/acs/SciMeetings-ACSSpring2020-HowToGuide_M3020-Final.pdf)

[Frequently Asked Questions](https://storage.googleapis.com/dl.morressier.com/acs/SciMtng_ACSNMSp2020_FAQ_M3120_Final.pdf)

ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.