Search

A synthetic route for the preparation of alkynylated saturated N‐heterocycles via a sequential combination of a Shono oxidation and a gold(I)‐catalyzed alkynylation reaction has been developed. The electrochemical Shono oxidation allowed an efficient access to a variety of N,O‐acetals via a direct C−H bond functionalization of cyclic amines. The reaction conditions were amenable with functionalized pyrrolidine, tetrahydroisoquinoline and pyrrolidine‐cyclopropyl fused bicyclic skeletons. The gold‐catalyzed process allowed the introduction of aryl acetylene partners bearing electron‐donating and moderate electron‐withdrawing. The efficiency of the gold process is remarkable and could be scaled up to 5 mmol of N,O‐acetal. Post‐functionalization reactions were performed based on the reactivity of the alkyne, showing the broad interest of our methodology. Promising preliminary results on an asymmetric version were obtained (e.r. up to 84.5:15.5). [ABSTRACT FROM AUTHOR]

Acenaphthylene carbaldehyde, tandem reaction, gold, C->O Rearrangement, HFIP Front Cover Picture: Gold-Catalyzed One-Pot Cycloisomerization/Nucleophilic Addition/Rearrangement of Acenaphthylene Carbaldehyde Derivatives (Adv. Keywords: Acenaphthylene carbaldehyde; tandem reaction; gold; C->O Rearrangement; HFIP EN Acenaphthylene carbaldehyde tandem reaction gold C->O Rearrangement HFIP 1907 1907 1 06/30/23 20230620 NES 230620 The front cover picture is an artistic illustration of gold associated with HFIP, represented by a golden ball surrounded with a banner. [Extracted from the article]