Advances in the Synthesis of Cyclopropylamines

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: March 6, 2025

Cyclopropylamines are an important subclass of substituted cyclopropanes that combine the unique electronic and steric properties with presence a donor nitrogen atom. In addition to their in diverse array biologically active compounds, cyclopropylamines utilized as synthetic intermediates, particularly ring-opening or cycloaddition reactions. Consequently, synthesis these compounds has constituted significant research topic, evidenced by abundant published methods. widely used Curtius rearrangement, classical cyclopropanation methods have been adapted integrate function (Simmons-Smith reaction, metal-catalyzed reaction diazo on olefins, Michael-initiated ring-closure reactions) advances enantioselective synthesis. More recently, specific developed for preparation aminocyclopropane moiety (Kulinkovich reactions applied amides nitriles, cyclopropenes, involving C-H functionalization, ...). The topic this review is present different cyclopropylamine derivatives, aim covering methodological best possible, highlighting scope, stereochemical aspects future trends.

Language: Английский

---

An Efficient Synthesis of 3,5-Bis-Aminated Pyrazolo[1,5-a]Pyrimidines: Microwave-Assisted Copper Catalyzed C-3 Amination of 5-Amino-3-Bromo-Substituted Precursors

Molecules, Journal Year: 2025, Volume and Issue: 30(3), P. 458 - 458

Published: Jan. 21, 2025

An efficient method has been developed for the rapid production of diverse arrays 3,5-bis-aminated pyrazolo[1,5-a]pyrimidines. The utilizes CuI (5 mol%) and carbazole-based ligand L-1 (N-(9H-carbazol-9-yl)-1H-pyrrole-2-carboxamide) (10 Ullmann-type coupling various amines to 5-amino-3-bromopyrazolo[1,5-a]pyrimidine precursors after heating in diethylene glycol (DEG) only 1 h at 80 °C (microwave heating). 3,5-Bis-aminated products were obtained good excellent yields (60–93%, 83% average 29 examples). 1° 2° alkylamines, as well a variety aryl- or heteroarylamines coupled efficiently, alkyl (or aryl) C-5 tolerated. optimized conditions worked on both 50 mg 1.0 g scales gave two steps from commercially available 3-bromo-5-chloropyrazolo[1,5-a]pyrimidine. Advantages provided by this include short reaction time, yields, broad substrate scope, avoidance toxic reagents commonly utilized reductive aminations C-3 NH2 substituted precursors.

Language: Английский

---

Nitrocyclopropanes as Valuable Building Blocks in Organic Synthesis and Biology: Exploring the Origin of the Nitro Group

Chemistry - A European Journal, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 30, 2025

Cyclopropane derivatives serve as important building blocks in organic synthesis, due to their three-membered stretched ring. Nitro-substituted cyclopropanes (NCPs) represent a special class of donor-acceptor (DACs) that contain strong electron-withdrawing nitro group substituent on the cyclopropyl moiety. Due versatile nature group, which can be converted into other functional azo groups or heterocyclic scaffolds, NCPs are considered design complex compounds. Herein, present review is organized two main sections focused synthesis and application NCPs. The part containing synthetic methodologies has been further divided distinct based mainly starting materials, such as: a) from nitroalkenes, b) nitro-bearing diazo compounds, c) nitroalkanes combination with alkenes, d) aminocyclopropanes under oxidative conditions, e) various through miscellaneous processes. In concerning applications use NCPs, categorization includes three subcategories, reduction 1-aminocyclopropane-1-carboxylic acids (ACC), ring opening leading valuable open-chain heterocycles, expansion larger cyclic

Language: Английский

---

Assembly of Biaryl Amines via Mild Copper-Catalyzed Coupling of Anilines with (Hetero)aryl Chlorides/Bromides

Organic Letters, Journal Year: 2025, Volume and Issue: 27(6), P. 1498 - 1503

Published: Jan. 31, 2025

CuI/6-hydroxy picolinohydrazide-catalyzed coupling of (hetero)aryl chlorides with anilines proceeded well at 100 °C to afford biaryl amines in a diverse manner, which represents the first example Cu-catalyzed under milder conditions. The same catalytic system could make bromides work room temperature, giving corresponding products an excellent reaction scope.

Language: Английский

---

CuSO₄/N-(9H-carbazol-9-yl)picolinamide-Catalyzed C–O Coupling of (Hetero)Aryl Chlorides with Phenols on Water

Organic Letters, Journal Year: 2024, Volume and Issue: 26(34), P. 7202 - 7206

Published: Aug. 21, 2024

A Cu-catalyzed C–O coupling of (hetero)aryl chlorides with phenols at 120 °C on water was developed a designed ligand, N-(9H-carbazol-9-yl)picolinamide (L2). This method features good substrate scope (both electron-donating and electron-withdrawing), low catalyst/ligand loadings (down to 1 mol %), excellent scalability practicability.

Language: Английский

---

Recent Advances in Nonprecious Metal Catalysis

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 7, 2024

As the field of nonprecious metal catalysis continues to expand, we pursue a review series covering selected transformations in this area over short time interval highlight practical advancements. We seek raise awareness both current art and need continue development toward broader applications earth-abundant metals chemical pharmaceutical industries.

Language: Английский

---

Recent Advances in (Di)Azafluorene Chemistry (A Review)

Russian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 60(11), P. 2086 - 2107

Published: Nov. 1, 2024

Language: Английский

---