Recent advances in oxidative radical difunctionalization of N-arylacrylamides enabled by carbon radical reagents

• Jiangfei Chen,
• Yi-Lin Qu,
• Ming Yuan,
• Xiang-Mei Wu,
• Heng-Pei Jiang,
• Ying Fu and
• Shengrong Guo

Beilstein J. Org. Chem. 2025, 21, 1207–1271, doi:10.3762/bjoc.21.98

• -free synthetic method for 3,3-disubstituted oxindoles via 1,2-alkylarylation of activated alkenes with alcohols [4]. N-Arylacrylamides and simple alcohols were employed as substrates, proceeding through an oxidative radical cyclization mechanism. The standard reaction conditions involved the use of an

• . Primary, secondary, and tertiary alkyl chlorides participated efficiently in the reaction, yielding 3,3-disubstituted oxindoles 81a–h in moderate to excellent yields of 40–92%. Notably, multichlorinated compounds, such as dichloromethane (DCM) and chloroform (CHCl₃), also served as effective alkylating

• halogenated oxindole product. In 2023, Kuniyil and Yatham’s group reported a redox-neutral, metal-free radical cascade cyclization strategy for the functionalization of N-arylacrylamides using unactivated alkyl and aryl chlorides, enabling the efficient construction of 3,3-disubstituted oxindoles 92 under

Synthetic applications of the Cannizzaro reaction

• Bhaskar Chatterjee,
• Dhananjoy Mondal and
• Smritilekha Bera

Beilstein J. Org. Chem. 2024, 20, 1376–1395, doi:10.3762/bjoc.20.120

• Cannizzaro reaction. Microwave-assisted crossed-Cannizzaro reaction for the synthesis of 3,3-disubstituted oxindoles. Synthesis of porphyrin-based rings using the Cannizzaro reaction. Synthesis of phthalides and pestalalactone via Cannizarro–Tishchenko-type reaction. Synthesis of dibenzoheptalene bislactones

Recent advancements in iodide/phosphine-mediated photoredox radical reactions

• Tinglan Liu,
• Yu Zhou,
• Junhong Tang and
• Chengming Wang

Beilstein J. Org. Chem. 2023, 19, 1785–1803, doi:10.3762/bjoc.19.131

• -heterocycles. Recently, independent research groups led by Li, Yang, and Patureau separately disclosed a novel approach to 3,3-disubstituted oxindoles 43 through an iodide/phosphine-catalyzed visible-light-mediated decarboxylative radical cascade cyclization of N-arylacrylamides 42 (Scheme 18) [35][36

Unexpected chiral vicinal tetrasubstituted diamines via borylcopper-mediated homocoupling of isatin imines

• Marco Manenti,
• Leonardo Lo Presti,
• Giorgio Molteni and
• Alessandra Silvani

Beilstein J. Org. Chem. 2022, 18, 303–308, doi:10.3762/bjoc.18.34

• commonly utilized as key intermediates for the synthesis of boron-containing peptidomimetics, which have been demonstrated to be efficient covalent ligands and valuable protease inhibitors endowed with various biological activities [5][6]. Going on with our interest in the synthesis of 3,3-disubstituted

• oxindoles [7][8][9][10][11] and also of aminoboronic acids [12], we recently exploited a molecular hybridization strategy to synthesize chiral oxindole-based β-aminoboronic acids and spiro derivatives [13]. Apart from our work and a quite recent report describing a useful Cu-catalyzed enantioselective

Enantioselective addition of diphenyl phosphonate to ketimines derived from isatins catalyzed by binaphthyl-modified organocatalysts

• Hee Seung Jang,
• Yubin Kim and
• Dae Young Kim

Beilstein J. Org. Chem. 2016, 12, 1551–1556, doi:10.3762/bjoc.12.149

• -disubstituted oxindoles bearing a quaternary stereogenic center at the C3-position have been reported to be biologically active against a variety of targets [17][18][19]. Consequently, the asymmetric synthesis of 3,3-disubstituted oxindole derivatives has received significant research attention over the past

• attention, and numerous catalytic enantioselective methods using chiral catalysts have been reported [9][10][11][12][13]. Oxindole and its derivatives can be exploited as important synthons to synthesize various alkaloid natural products and biologically active compounds [14][15][16]. In particular, 3,3

Catalytic asymmetric synthesis of biologically important 3-hydroxyoxindoles: an update

• Bin Yu,
• Hui Xing,
• De-Quan Yu and
• Hong-Min Liu

Beilstein J. Org. Chem. 2016, 12, 1000–1039, doi:10.3762/bjoc.12.98

• ., Sc(OTf)3, In(OTf)3, Zn(OTf)2, FeCl3, etc) can catalyze the reactions to give 3,3-disubstituted oxindoles in moderate to excellent yields and with excellent regioselectivities. For para-substituted phenols, the reactions gave the corresponding ortho-substituted products. While for para-unsubstituted

The aminoindanol core as a key scaffold in bifunctional organocatalysts

• Isaac G. Sonsona,
• Eugenia Marqués-López and
• Raquel P. Herrera

Beilstein J. Org. Chem. 2016, 12, 505–523, doi:10.3762/bjoc.12.50

• -diamino-3,3’-disubstituted-oxindoles 42. These are key intermediates for the preparation of biologically and pharmacologically attractive compounds, such as (+)-alantrypinone [45], (−)-serantrypinone [46] and (−)-lapatin [47]. In the presence of the catalyst 41 (10 mol %), a broad scope of the oxindoles

Primary-tertiary diamine-catalyzed Michael addition of ketones to isatylidenemalononitrile derivatives

• Akshay Kumar and
• Swapandeep Singh Chimni

Beilstein J. Org. Chem. 2014, 10, 929–935, doi:10.3762/bjoc.10.91

• -component version of the reaction by a domino Knoevenagel–Michael sequence. The Michael adduct 4a was transformed into spirooxindole 6 by a reduction with sodium borohydride in a highly enantioselective manner. Keywords: 3,3'-disubstituted oxindoles; Michael reaction; organocatalysis; primary-tertiary

• attention as novel substrates for the enantioselective synthesis of 3,3'-disubstituted oxindoles [18][19][20][21][22]. The organocatalytic Michael addition of ketones to isatylidenemalononitriles via enamine-catalysis has emerged as a useful tool for the synthesis of 3,3'-disubstituted oxindoles, which

• ][45]. We describe herein that a similar catalyst system could also efficiently catalyze the asymmetric Michael addition reaction between ketones 2 and isatylidenemalononitrile derivatives 3 to procure highly functionalized 3,3'-disubstituted oxindoles 4 which could easily be transformed into

Organocatalytic asymmetric Michael addition of unprotected 3-substituted oxindoles to 1,4-naphthoquinone

• Jin-Sheng Yu,
• Feng Zhou,
• Yun-Lin Liu and
• Jian Zhou

Beilstein J. Org. Chem. 2012, 8, 1360–1365, doi:10.3762/bjoc.8.157

• catalytic synthesis of which was unprecedented. Keywords: 3,3-disubstituted oxindoles; Michael addition; organocatalysis; quaternary stereogenic center; unprotected 3-substituted oxindoles; Introduction The catalytic asymmetric synthesis of 3,3-disubstituted oxindoles has recently received great attention

• biological activities [4]. Accordingly, the development of efficient synthetic methods to enable the synthesis of 3,3-disubstituted oxindoles in great structural diversity is of current interest, and much progress had been made in the catalytic enantioselective synthesis of 3-hydroxyoxindoles [5][6][7][8][9

• -disubstituted oxindoles, using cheap and easily available starting materials and simple chiral catalysts to facilitate biological evaluation. We have developed the catalytic asymmetric addition of acrolein, allyltrimethylsilane or difluoroenoxysilanes to isatins to furnish differently substituted