Rewriting Alkene Frameworks: A Practical Strategy for Nitrogen Incorporation

Abstract

Expanding the reach of skeletal editing to unactivated hydrocarbons presents a formidable challenge in nitrogen incorporation chemistry. In a recent advance, Morandi and coworkers have developed a direct, metal-free strategy to insert nitrogen into simple alkenes, converting them into valuable amidines and nitriles. This transformation leverages a transient aza-allenium intermediate, formed in situ from phenyliodine(III) bis(trifluoroacetate) and ammonium carbamate, to achieve CN bond formation under mild and open-flask conditions. The method is notable for its broad substrate scope, high yields (up to 99%), and compatibility with diverse functional groups—including esters, ketones, halides, and alcohols. Crucially, it marks a conceptual departure from earlier indole-based editing strategies by engaging electronically unbiased alkenes. Through operational simplicity and mechanistic novelty, this work defines a new direction for nitrogen insertion chemistry and opens avenues for late-stage functionalization and modular scaffold diversification.