Aromatic C–H bond functionalization through organocatalyzed asymmetric intermolecular aza-Friedel–Crafts reaction: a recent update

• Anup Biswas

Beilstein J. Org. Chem. 2023, 19, 956–981, doi:10.3762/bjoc.19.72

• substrates (see transition state 75, Scheme 18). This C–C-bond formation affords a 3-indolinone moiety bearing an aza-quaternary stereocenter at the C2 position. In addition, the reaction allows to obtain axially chiral products 70/72/74 through restriction of the C–C bond rotation around the heteroaryl and

Synthetic strategies for the preparation of γ-phostams: 1,2-azaphospholidine 2-oxides and 1,2-azaphospholine 2-oxides

• Jiaxi Xu

Beilstein J. Org. Chem. 2022, 18, 889–915, doi:10.3762/bjoc.18.90

• important five-membered azaphosphaheterocycles, They are known as γ-phostams, including γ-phosphonolactams and γ-phosphinolactams. Benzo[1,2]azaphospholine 2-oxides are phosphorus analogues of indolinone derivatives and show important biological activities. Both γ-phosphonolactams and γ-phosphinolactams and

Controlling alkyne reactivity by means of a copper-catalyzed radical reaction system for the synthesis of functionalized quaternary carbons

• Goki Hirata,
• Yu Yamane,
• Naoya Tsubaki,
• Reina Hara and
• Takashi Nishikata

Beilstein J. Org. Chem. 2020, 16, 502–508, doi:10.3762/bjoc.16.45

• . Moreover, the reaction of α-bromocarbonyl compound 2 and an alkyne 4 possessing a carboxamide moiety undergoes tandem alkyl radical addition/C–H coupling to produce indolinone derivative 5. Keywords: copper catalyst; 1,3-enyne; functionalized quaternary carbon; indolinone; tandem alkyl radical addition

• Pd-catalyzed cascade reaction (C–C bond formation/C–H cyclization process) of N-arylpropynamide 4 for the preparation of indolinone derivatives 5 was previously reported by Li’s group [34][35]. In another report on C–H cyclization by Lei’s group, Ni-catalyzed aromatic C–H alkylation occurs via a

• addition at a C–C triple bond followed by Sonogashira coupling to produce 1,3-enyne compounds. On the other hand, the reaction with alkyne possessing a carboxamide moiety underwent tandem alkyl radical addition at the C–C triple bond followed by C–H coupling to produce indolinone derivatives. These results

Methyl isocyanide as a convertible functional group for the synthesis of spirocyclic oxindole γ-lactams via post-Ugi-4CR/transamidation/cyclization in a one-pot, three-step sequence

• Amarendar Reddy Maddirala and
• Peter R. Andreana

Beilstein J. Org. Chem. 2018, 14, 875–883, doi:10.3762/bjoc.14.74

• thought of as a synthetic equivalent to ‘CO’ for insertion into the 2-indolinone backbone (shown in Scheme 1). To further elaborate on this observation and for understanding the role of methyl isocyanide as a CIC, we designed an efficient synthetic strategy for spiro[indoline-3,2'-pyrrole]-2,5'(1'H

Recent developments in the asymmetric Reformatsky-type reaction

• Hélène Pellissier

Beilstein J. Org. Chem. 2018, 14, 325–344, doi:10.3762/bjoc.14.21

• ) and zinc in 2-Me-THF at 0 °C in the presence of CuCl. As shown in Scheme 13, a range of products 33a–m were obtained in both moderate to high yields (65–91%) and diastereoselectivities (70–96% de). Indeed, various substituents on each carbon (C4–C7) of the indolinone ring, such as halides, alkyl

Synthesis of a deuterated probe for the confocal Raman microscopy imaging of squalenoyl nanomedicines

• Eric Buchy,
• Branko Vukosavljevic,
• Maike Windbergs,
• Dunja Sobot,
• Camille Dejean,
• Simona Mura,
• Patrick Couvreur and
• Didier Desmaële

Beilstein J. Org. Chem. 2016, 12, 1127–1135, doi:10.3762/bjoc.12.109

• induced focal cerebral ischemia and in rats undergoing spinal cord injury [16]. Interestingly, the “squalenisation platform” initially developed with highly hydrophilic therapeutics has been further extended to hydrophobic drugs such as beta-lactam antibiotics [17], paclitaxel [18], indolinone kinase

Study on the synthesis of the cyclopenta[f]indole core of raputindole A

• Nils Marsch,
• Mario Kock and
• Thomas Lindel

Beilstein J. Org. Chem. 2016, 12, 334–342, doi:10.3762/bjoc.12.36

• . Alternatively, for a similar 1,3-shift, Nolan and coworkers proposed two sequential 1,2-shifts to occur after π-complexation of the triple bond by Au(I) [49]. Methanolysis (NaOMe/MeOH) of cyclopentenylacetate 50 afforded cyclopenta[f]indolinone 48 (96%). Conclusion It was our goal to explore how to efficiently

Recent advances in copper-catalyzed C–H bond amidation

• Jie-Ping Wan and
• Yanfeng Jing

Beilstein J. Org. Chem. 2015, 11, 2209–2222, doi:10.3762/bjoc.11.240

• undertake the amidation to provide indolinone product 28''. An important factor enabling the C–H bond transformation was the presence of the quinoline auxiliary which acted as a bidentate fragment to incorporate the copper catalyst and facilitate the bond cleavage and formation via intermediates A and B

Novel indolin-2-one-substituted methanofullerenes bearing long n-alkyl chains: synthesis and application in bulk-heterojunction solar cells

• Irina P. Romanova,
• Andrei V. Bogdanov,
• Inessa A. Izdelieva,
• Vasily A. Trukhanov,
• Gulnara R. Shaikhutdinova,
• Dmitry G. Yakhvarov,
• Shamil K. Latypov,
• Vladimir F. Mironov,
• Vladimir A. Dyakov,
• Ilya V. Golovnin,
• Dmitry Yu. Paraschuk and
• Oleg G. Sinyashin

Beilstein J. Org. Chem. 2014, 10, 1121–1128, doi:10.3762/bjoc.10.111

• popular fullerene derivative in organic photovotaics is (PCBM) [4][5][6]. As an alternative to PCBM, we recently suggested indolinone-substituted methanofullerenes (IM) [7]. The principal advantages of IM are their easier synthesis and purification as compared to PCBM [7][8]. Indeed, the IM can be

• ). Note that, for the wavelengths shorter than 600 nm, the AIM absorption is stronger than that of PCBM and fullerene C60 that could be assigned to the effect of the indolinone fragment. To evaluate the stability of reduced AIMs and the AIM LUMO energy levels, a CV study was performed. Four reversible

• peaks are observed in the CV data of AMF 1–9. Table 1 summarizes the results, and Figure 3 presents a typical CV curve of AIM. Note that both the fullerene sphere and the indolinone fragment are electrochemically active in the working electrochemical window. Thus, the pristine fullerene C60 and isatins

Recent applications of the divinylcyclopropane–cycloheptadiene rearrangement in organic synthesis

• Sebastian Krüger and
• Tanja Gaich

Beilstein J. Org. Chem. 2014, 10, 163–193, doi:10.3762/bjoc.10.14

• oxindole was crucial for the stereochemical control of the spiro-indolinone system in 138, it was removed in the next step using radical conditions. Horner–Wadsworth–Emmons olefination on the carbonyl moiety followed by protection of the oxindole gave intermediate 139. Conjugate addition of methylamine and

An overview of the key routes to the best selling 5-membered ring heterocyclic pharmaceuticals

• Marcus Baumann,
• Ian R. Baxendale,
• Steven V. Ley and
• Nikzad Nikbin

Beilstein J. Org. Chem. 2011, 7, 442–495, doi:10.3762/bjoc.7.57

• normally filled by the ADP’s adenine in the phosphorylated protein. The indolinone section is located in a deeper pocket with the heteroatoms being involved in H-bonding glutamate and tyrosine residues whilst the pyrrole ring and the diethylaminoethyl appendage are exposed to the solvent environment [8

• ] (Figure 3). Structurally, this medication consists of a complex pyrrole-substituted 2-indolinone core which can be prepared by a late stage aldol condensation between a 2-indolinone fragment 42 with the corresponding pyrrole aldehyde 41 (Scheme 7). The oxime functionality in compound 38, which is obtained