1,5,7-Triazabicylodec-5-ene-Promoted Direct Vinylogous Aldol Reaction for the Synthesis of 3-Hydroxy-2-oxoindole Derivatives

Abstract

A simple and efficient method has been developed for the synthesis of 3-hydroxy-2-oxoindole derivatives through a direct vinylogous aldol reaction of allylic esters with isatins, catalyzed by 1,5,7-triazabicyclodec-5-ene. This method affords a variety of 3-hydroxy-2-oxoindole derivatives in moderate to excellent yields with high regioselectivities. An asymmetric version of this reaction catalyzed by Corey’s chiral guanidine proceeded with moderate enantioselectivity. The protocol can also be used to synthesize isatin spiro ethers.

Key words

hydroxyoxoindoles - vinylogous aldol reaction - triazabi­cyclododecene - isatins - isatin spiro ethers - asymmetric catalysis

• References and Notes

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• 18 Benzyl (2E)-4-(3-Hydroxy-2-oxo-2,3-dihydro-1H-indol-3-yl)but-2-enoates 3; General Procedure A clean septum-capped vial equipped with a stirring bar was charged with the appropriate isatin 1 (0.1 mmol), ester 2 (0.2 mmol), TBD (0.02 mmol), and anhyd THF (1 mL), and the mixture was heated to 40 °C until the starting material was fully consumed (TLC). The solvent was removed under reduced pressure, and the residue was purified by column chromatography [silica gel, EtOAc–hexane (6:1)]. Benzyl (2E)-4-(3-Hydroxy-1-methyl-2-oxo-2,3-dihydro-1H-indol-3-yl)but-2-enoate (3a) White solid; yield: 29.3 mg (87%). ¹H NMR (600 MHz, CDCl₃): δ = 7.36–7.26 (m, 7 H), 7.11–7.09 (t, J = 7.6 Hz, 1 H), 6.89–6.83 (m, 2 H), 5.91–5.88 (d, J = 15.6 Hz, 1 H), 5.13 (s, 2 H), 3.47 (s, 1 H), 3.16 (s, 3 H), 2.91–2.88 (m, 1 H), 2.70–2.67 (m, 1 H). ¹³C NMR (150 MHz, CDCl₃): δ = 177.6, 165.7, 143.1, 141.6, 136.0, 130.1, 129.2, 128.6, 128.3, 128.2, 125.6, 124.4, 123.5, 108.8, 75.8, 66.2, 41.1, 26.4. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₀H₂₀NO₄: 338.1387; found: 338.1385.