A Rapid and Highly Efficient One-Pot Methodology for Preparation of Alkyl Oxindolideneacetates

Abstract

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When Ethyl Isocyanoacetate Meets Isatins: A 1,3-Dipolar/Inverse 1,3-Dipolar/Olefination Reaction for Access to 3-Ylideneoxindoles

“…The reported synthetic methods for 3-ylideneoxindoles can be typically classified into two classes. The first class mainly focuses on the utility of isatins as building blocks through the Wittig reaction (Scheme a,b). , Another class involves base-mediated phenoxide cyclization or palladium-catalyzed aromatic C–H functionalization (Scheme c,d). , Although these methods are efficient, they suffer from some difficulties such as use of hazardous or toxic reagents, generating much waste and poor atom economy, or the use of expensive palladium catalysts and requirement of elaborately designed or inaccessible substrates, which limit their application.…”

Steric-Hindrance-Induced Diastereoselective Radical Nitration of 3-Alkylidene-2-oxindoles Followed by Tosylhydrazine-Mediated Sulfonation

“…(E)-Ethyl 2-(5-chloro-2-oxoindolin-3-ylidene)acetate (4c). 24 Orange crystalline solid, mp = 160−162 °C; yield: 436 mg, 87%; 1 H NMR (300 MHz, ): δ = 10.93 (s, 1H), 8.38 (s, 1H), 7.42−7.39 (m, 1H), 6.93−6.86 (m, 1H), 6.62 (s, 1H), 4.28 (d, J = 6.9 Hz, 2H), 1.30 (t, J = 6.9 Hz, 3H); 13 C { 1 H} NMR (75 MHz,165.4,144.3,137.9,133.8,128.0,126.2,122.8,121.4,114.3,112.2,61.7,14.4.…”

“…Orange liquid; yield: 419 mg, 81%; 1 H NMR (300 MHz, CDCl 3 ): δ = 8.56 (d,J = 7.8 Hz,1H),7.34 (t,J = 7.8 Hz,1H),7.04 (t,J = 7.8 Hz,1H),6.90 (s,1H),6.80 (d,J = 7.8 Hz,1H), 4.32 (q, J = 6.6 Hz, 2H), 3.69 (t, J = 6.6 Hz, 2H), 1.71 (q, J = 7.2 Hz, 2H), 1.37 (t, J = 7.2 Hz, 3H), 0.96 (t, J = 7.2 Hz, 3H); 13 C { 1 H} NMR (75 MHz,CDCl 3 ) d: δ = 167.4,165.6,145.4,137.8,132.2,128.7,122.5,122.2,119.9,108.3,61.0,41.6,20.7,14.1,11. (E)-Ethyl 2-(5-bromo-2-oxoindolin-3-ylidene)acetate (4e). 24 Orange crystalline solid, mp = 207−208 °C; yield: 507 mg, 86%; 1 H NMR (300 MHz, ): δ = 10.92 (s, 1H), 8.50 (s, 1H), 1H),6.82 (d,J = 8.1 Hz,1H),6.59 (s,1H), 4.28 (d, J = 6.9 Hz, 2H), 1.30 (t,J = 6.9 Hz, 3H); 13 C { 1 H} NMR (75 MHz,165.3,144.6,137.7,135.6,130.8,122.7,121.9,113.8,112.7,61.7,14.4.…”

“…(E)-Ethyl 2-(5-chloro-1-methyl-2-oxoindolin-3-ylidene)acetate (4f). 24 Orange crystalline solid, mp = 118−120 °C; yield: 424 mg, 80%; 1 H NMR (300 MHz, CDCl 3 ): δ = 8.60 (s, 1H), 7.36 (d,J = 8.1 Hz,1H),6.95 (s,1H),6.74 (d,J = 8.4 Hz,1H),4.36 (d,J = 7.2 Hz, 2H), 1.40 (t, J = 7.2 Hz, 3H); 13 C { 1 H} NMR (75 MHz, CDCl 3 ) d: δ = 167. 1, 165.3, 144.4, 136.9, 132.0, 128.9, 128.3, 123.9, 121.0, 109.0, 61.5, 28.4, 14.2 (E)-Ethyl 2-(5-nitro-2-oxoindolin-3-ylidene)acetate (4g).…”

Photochemical Aryl Radical Cyclizations to Give (E)-3-Ylideneoxindoles

“…3-Ylideneoxindoles, mainly ethyl (2 E )-(1-methyl-2-oxoindolin-3-ylidene)acetate ( 2a ) have recently become privileged precursors in organic synthesis for organocatalyzed asymmetric Michael additions/cyclization [1], epoxidation [2,3], reduction [4], [2+2] cycloaddition using visible light photocatalysis [5], and [3+2] cycloaddition sequences [6,7]. 2-Oxoindolin-3-ylidene acetate derivatives are prepared via modifications of the Wittig reaction on alkylated isatin (indole-2,3-dione) derivatives [3,7,8,9]. The 3-ylideneoxindole moiety is present in a number of natural products, pharmaceuticals and biologically important derivatives [10].…”