Spiro[indoline-3,4′-piperidine]
is a significant structural
scaffold in numerous polycyclic indole alkaloids with a variety of
bioactivities. In this study, a synthetic strategy was developed to
access spiro[indoline-3,4′-pyridin]-2-yl carbamate via an AgOTf/PPh3-catalyzed tandem cyclization of tryptamine-ynesulfonamides.
The unique feature of this strategy is the efficient intermolecular
capturing of the in situ generated spiroindoleninium intermediates
with carbamates, leading to the diastereoselective syntheses of spiro[indoline-3,4′-pyridin]-2-yl
carbamate derivatives. A broad scope of this cyclization was demonstrated
by a variety of tryptamine-ynesulfonamide substrates and several carbamates.
A plausible mechanism of this reaction was proposed.
N‐Fluorobenzenesulfonimide (NFSI), one of the most popular fluorinating agents in organic synthesis, was used as a ligand of silver triflate (AgOTf) to assist the trapping of the persistent spiroindoleninium intermediates by forming a weak noncovalent interaction between the substrate and metal ligand. The AgOTf/NFSI catalytic system was identified in the cycloisomerization of tryptamine‐ynamide to spiro[indoline‐3,4′‐piperidine] derivatives. The substrate tolerances were demonstrated by various synthetic substrates and commercially available nucleophiles. A cation‐π‐π model was proposed to elucidate the mechanism of action based on the experimental observations and density functional theory (DFT) calculations.
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