Aryne-mediated [2,3]-sigmatropic rearrangement of tertiary 2,3-allenylamines bearing an electron-withdrawing group at the α-position

An unprecedented [2,3]-sigmatropic rearrangement reaction of quaternary 2,3-allenylammonium ylides, generated in situ from tertiary 2,3-allenylamines and arynes, has been established. With 2-(trimethylsilyl)aryl triflates as aryne precursors, a range of tertiary 2,3-allenylamines bearing an electron-withdrawing group at the alpha-position smoothly participated in the aryne-mediated [2,3]-sigmatropic rearrangement at room temperature, delivering structurally diverse 2-vinylallyamines or 1-amino-1,3-dienes in moderate to excellent yields. The reaction proceeds in the absence of strong bases and transition metals, is compatible with moisture and air, and tolerates a wide variety of functional groups.

Automated summary

An unprecedented [2,3]-sigmatropic rearrangement reaction has been established using quaternary 2,3-allenylammonium ylides generated in situ from tertiary 2,3-allenylamines and arynes. The reaction, which proceeds smoothly at room temperature, delivers structurally diverse products in moderate to excellent yields and is tolerant to a wide variety of functional groups. This reaction is carried out without the need for strong bases or transition metals, making it a versatile and convenient method for organic synthesis.