C–H activation-initiated spiroannulation reactions and their applications in the synthesis of spirocyclic compounds

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(12), P. 2324 - 2338

Published: Jan. 1, 2024

This review summarizes the most recent progress made in C–H bond activation-initiated spiroannulation reactions and their applications construction of structurally diverse biologically valuable spirocyclic scaffolds.

Language: Английский

---

Expeditious Synthesis of Spiroindoline Derivatives via Tandem C(sp²)–H and C(sp³)–H Bond Functionalization of N-Methyl-N-nitrosoanilines

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3091 - 3096

Published: April 3, 2024

Presented herein is a novel synthesis of pharmaceutically privileged spiroindoline derivatives via cascade reactions N-methyl-N-nitrosoanilines with diazo homophthalimides. A group mechanistic studies disclosed that the formation product involves an unusual reaction mode N-methyl-N-nitrosoaniline featuring initial C(sp2)–H bond activation/alkylation followed by C(sp3)–H activation/spiroannulation. To our knowledge, this first example in which acts as C3N1 synthon to accomplish formal [4+1] spiroannulation participation N-methyl unit rather than previously reported C2N1 undergo [3+2] annulation without unit. In general, newly developed synthetic protocol features simple and readily accessible starting materials, valuable products, unique mechanism, high efficiency atom-economy, excellent compatibility diverse functional groups, ready scalability.

Language: Английский

---

Copper-catalyzed divergent construction of naphthofurans and benzochromanes from 2-naphthols, 4-methylene-quinazolin(thi)ones, and N,N-dimethylethanolamine

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(4), P. 1198 - 1204

Published: Jan. 1, 2024

Cu( ii )-catalyzed divergent synthesis of naphthofurans and benzochromanes through [3 + 2 1] 1 annulations is established.

Language: Английский

---

Synthesis of functionalized quinolines from the cascade reactions of N-aryl amidines with two CF₃-ynones via C–H/N–H/C–N/C–C bond cleavage

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(7), P. 1917 - 1923

Published: Jan. 1, 2024

We present a novel synthesis of CF 3 - and alkynyl-substituted quinoline derivatives based on Rh( iii )-catalyzed cascade reactions N -aryl amidines with two -ynones. Then, some products are transformed into polycyclic -benzo[ k ]phenanthridines through an intramolecular annulation reaction.

Language: Английский

---

Synthesis of 1,7-Fused Indolines Tethered with Spiroindolinone Based on C–H Activation Strategy with Air as a Sustainable Oxidant

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(3), P. 1880 - 1897

Published: Jan. 22, 2024

Herein, we present an efficient synthesis of 1,7-fused indolines tethered with a spiroindolinonyl moiety through the cascade reaction indolin-1-yl(aryl)methanimines diazo oxindoles. To best our knowledge, this is first example in which indoline skeleton was constructed along simultaneous introduction spiro element initiated by C–H bond activation indoline. In forming title product, substrate and coupling partner demonstrated unprecedented pattern latter acts as C1 synthon to participate construction spirocyclic scaffold reductive elimination key seven-membered Ru(II) species using air effective sustainable oxidant regenerate active catalyst. Moreover, studies on cytotoxicity selected products against several human cancer cell lines their potential lead compounds for development anticancer drugs. With notable features such simple economical substrates, pharmaceutically valuable sophisticated skeleton, mild conditions, cost-free oxidants, high efficiency, excellent compatibility diverse functional groups, scalability, method expected find wide applications related areas.

Language: Английский

---

Synthesis of Indenone-Fused Pyran Derivatives from Aryl Enaminones and Cyclopropenones through Unsymmetrical Relay C–H Bond Activation and Double C–C/C–O Bond Formation

Organic Letters, Journal Year: 2024, Volume and Issue: 26(31), P. 6602 - 6607

Published: July 30, 2024

Presented herein is a novel synthesis of indenone-fused pyran derivatives via the cascade reactions aryl enaminones with cyclopropenones. The formation products involves one-pot procedure consisting C–H bond and enamine functionalization along C–C cleavage cyclopropenone 1,3-rearrangement in situ-formed allylic alcohol moiety followed by intramolecular O-nucleophilic addition Me2NH elimination. To our knowledge, this first simultaneous both indenone scaffolds through concurrent unsymmetrical relay activation double C–C/C–O formation. Moreover, usefulness method further showcased its suitability for large-scale synthetic scenarios diverse transformations products.

Language: Английский

---

Solvent-Dependent Selective Synthesis of CF₃-Tethered Indazole Derivatives Based on Multiple Bond Activations

Organic Letters, Journal Year: 2023, Volume and Issue: 25(5), P. 720 - 725

Published: Jan. 27, 2023

Presented herein is a solvent-dependent selective synthesis of CF3-tethered indazole derivatives via the cascade reactions 1-arylpyrazolidinones with trifluoromethyl ynones. Mechanistically, formation title products involves N–H/C–H/C–N/C–C bond cleavage along pyrazole ring and pyrazolidinone opening. For scaffold, 1-phenylpyrazolidinone acts as C2N2 synthon, while ynone serves C1 synthon. Meanwhile, also an enol unit to facilitate opening provide trifluoropropenoxy fragment alkynyl triple migration cleaved moiety. When reaction was run in trifluoroethanol instead DCE, it selectively afforded tethered trifluoroethoxy moiety through situ transesterification. To our knowledge, this first concurrent activation, formation, CF3 migration.

Language: Английский

---

Unsymmetrical relay C–H alkenylation and [2 + 2] cycloaddition ofN-arylsydnones with allenyl acetates leading to quinoline-fused cyclobutanes

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(5), P. 1191 - 1197

Published: Jan. 1, 2023

In this paper, we present a direct, effective and atom-economical access toward quinoline-fused cyclobutane derivatives through Rh( iii )-catalyzed cascade reactions of N -arylsydnones with allenyl acetates.

Language: Английский

---

Synthesis of homophthalimide spironaphthalenones through [5 + 1] spiroannulation of aryl/alkenyl enaminones with diazo homophthalimides

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(17), P. 4282 - 4288

Published: Jan. 1, 2023

Presented herein is a novel synthesis of homophthalimide spironaphthalenones from the cascade reaction enaminones with diazo homophthalimides.

Language: Английский

---

Synthesis of N-Arylindoles from 2-Alkenylanilines and Diazonaphthalen-2(1H)-ones through Simultaneous Indole Construction and Aryl Introduction

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(11), P. 7392 - 7404

Published: May 20, 2022

In this paper, an efficient synthesis of N-arylindoles through the cascade reaction 2-alkenylanilines with diazonaphthalen-2(1H)-ones is presented. Mechanistically, involves generation a Ru-carbene complex from diazonaphthalen-2(1H)-one, followed by carbene N-H bond insertion 2-alkenylaniline, intramolecular cyclization, and oxidative aromatization. reaction, Ru(II) acts as multifunctional catalyst to promote not only formation but also cyclization dehydrogenative Meanwhile, air green cost-effective oxidant. To our knowledge, first example in which were synthesized simultaneous introduction N-aryl unit construction indole scaffold. Notable advantages method include readily accessible halide-free substrates, additive-free conditions, good efficiency, excellent atom economy, compatibility diverse functional groups. addition, utility product thus obtained was showcased its structural transformations.

Language: Английский

---