The asymmetric allylic alkylation (AAA) reaction lies amongst the most powerful strategies for the catalytic construction of C-C bonds in stereoselective manner. The pioneering works of Trost on the Pd-catalyzed AAA, together with the seminal reports of Kim and Lu on the organic Lewis base catalyzed AAA of Morita-Baylis-Hillman (MBH) derivatives, established the foundations of both the transition-metal catalyzed and the organocatalytic versions. Since then, extensive efforts have been devoted to expanding their generality and harness their asymmetric potential. Yet, these transformations are mainly restricted to the use of acidic or stabilized C-nucleophiles, such as alkali-metal salts, active methylene compounds or enolates. Conversely, the use of non-acidic or non-stabilized nucleophiles in asymmetric allylic alkylation remains largely underdeveloped. Photochemistry is currently emerging as a complementary and more sustainable approach in synthetic chemistry. The unprecedented reactivity of excited organic molecules under light irradiation has tremendously expanded the playground for new reaction discovery. Herein is presented the asymmetric allylic benzylation of racemic MBH carbonates with 2-methyl benzophenone derivatives as non-stabilized benzylating C-nucleophiles. The dual activation of both reaction partners, chiral Lewis-base activation of the electrophile and light-activation of the nucleophile, enables the stereoselective installation of benzyl groups at allylic positions for the construction of tertiary and quaternary carbon centers.

Light-triggered catalytic asymmetric allylic benzylation with photogenerated C-nucleophiles

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.