Alkyl nitriles are a versatile synthetic intermediate that are frequently embedded in an array of bioactive natural products and pharmaceuticals, in addition to being versatile synthetic intermediates. Nevertheless, methods for their selective incorporation are underdeveloped in comparison with related motifs, namely, aldehydes, ketones, esters, amides, <i>etc.</i> Consequently, the ability to readily employ alkyl nitriles as pronucleophiles in asymmetric transition metal catalysis is highly desirable, albeit challenging because of the nature and reactivity of the anion. This presentation will describe the development of a highly regioselective and stereospecific rhodium-catalyzed cyanomethylation of tertiary allylic carbonates to construction acyclic β-quaternary stereogenic nitriles, which permits access to several carbonyl derivatives that are challenging to prepare using conventional pronucleophiles. The synthetic utility of the stereospecific cyanomethylation is further highlighted through derivations of the nitrile group, one of which provides formal syntheses of two natural products.

Regioselective and stereospecific allylic cyanomethylation: Construction of acyclic β-quaternary stereogenic nitriles

Fall 2022 abstracts, posters, and presentations will launch in mid-September.

ACS Fall 2022

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