Iron(II)‐Catalyzed 1,2‐Diamination of Styrenes Installing a Terminal NH2 Group Alongside Unprotected Amines DOI Creative Commons
Valentyn Pozhydaiev,

Antonio Paparesta,

Joseph Moran

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(45)

Опубликована: Июль 17, 2024

Abstract 1,2‐Diamination of alkenes represents an attractive way to generate differentiated vicinal diamines, which are prevalent motifs in biologically active compounds and catalysts. However, existing methods usually limited scope produce diamines where one or both nitrogens protected, adding synthetic steps for deprotection further N‐functionalization reach a desired target. Furthermore, the range amino groups that can be introduced at internal position is fairly limited. Here we describe 1,2‐diamination styrenes directly installs free group terminal wide variety unprotected nitrogen nucleophiles (primary secondary alkyl aromatic amines, sulfoximines, N ‐heterocycles, ammonia surrogate) position. Two complementary sets conditions encompass electronically activated deactivated with diverse substitution patterns functional groups. Moreover, this strategy extended 1,2‐aminothiolation styrenes.

Язык: Английский

Iron-catalyzed fluoroalkylative alkylsulfonylation of alkenes via radical-anion relay DOI Creative Commons
Xiaoya Hou, Hongchi Liu, Hanmin Huang

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Фев. 17, 2024

Abstract Transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides is a powerful method for upgrading commodity chemicals into densely functionalized molecules. However, super stoichiometric amounts metal reductant and the requirement installing directing group to suppress inherent β-H elimination bring great limitations this type reaction. We demonstrate herein that two different accessible via radical-anion relay Na 2 S O 4 as both sulfone-source. The together electron-shuttle catalyst crucial divert mechanistic pathway toward formation sulfone anion instead previously reported alkylmetal intermediates. Mechanistic studies allow identification carbon-centered radical sulfur-centered radical, which are in equilibrium capture or extrusion SO could be converted accelerated by iron catalysis, leading observed high chemoselectivity.

Язык: Английский

Процитировано

26
TBADT‐Mediated Photocatalytic Stereoselective Radical Alkylation of Chiral N‐Sulfinyl Imines: Towards Efficient Synthesis of Diverse Chiral Amines DOI Creative Commons
Matteo Leone, Joseph P. Milton, Dorota Gryko

и другие.

Chemistry - A European Journal, Год журнала: 2024, Номер 30(24)

Опубликована: Фев. 20, 2024

Abstract Herein we describe a sustainable and efficient photocatalytic method for the stereoselective radical alkylation of chiral sulfinyl imines. By employing readily available non‐prefunctionalized precursors cost‐effective TBADT as direct HAT photocatalyst, successfully obtain diverse amines with high yields excellent diastereoselectivity under mild conditions. This provides an approach accessing array medicinally relevant compounds, including both natural synthetic α‐amino acids, aryl ethyl amines, other structural motifs commonly found in approved pharmaceuticals product.

Язык: Английский

Процитировано

13
Remote Radical 1,3-, 1,4-, 1,5-, 1,6- and 1,7-Difunctionalization Reactions DOI Creative Commons
Xiaoming Ma, Qiang Zhang, Wei Zhang

и другие.

Molecules, Год журнала: 2023, Номер 28(7), С. 3027 - 3027

Опубликована: Март 28, 2023

Radical transformations are powerful in organic synthesis for the construction of molecular scaffolds and introduction functional groups. In radical difunctionalization reactions, radicals first functionalized intermediates can be relocated through resonance, hydrogen atom or group transfer, ring opening. The resulting undertake following paths second functionalization: (1) couple with other groups, (2) oxidize to cations then react nucleophiles, (3) reduce anions electrophiles, (4) metal-complexes. rearrangements provide opportunity 1,3-, 1,4-, 1,5-, 1,6-, 1,7-difunctionalization products. Multiple ways initiate reaction coupling intermediate make reactions good at remote positions. These offer advantages synthetic efficiency, operation simplicity, product diversity.

Язык: Английский

Процитировано

21
Enantioselective Divergent Syntheses of Cephalotaxus Alkaloids: (−)-Cephalotaxine, (−)-Cephalotine B, and (−)-Fortuneicyclidins A and B DOI
Xian‐Tao An,

Xiao‐Min Ge,

Xinyu Liu

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(16), С. 9233 - 9241

Опубликована: Апрель 12, 2023

A new strategy focusing on the last-stage asymmetric assembly of ring D, which inherently possesses densest part stereogenic centers and functional groups in A/B/C/D system (-)-cephalotaxine, has been developed, a novel Rh-catalyzed (2 + 3) annulation tertiary enamides with enoldiazoacetates is designed explored for enantioselective construction crucial cyclopentane D bearing unique spirocyclic aza-quaternary stereocenter. Based expeditious access chiral functionalized building block tetracyclic system, concise total synthesis (-)-cephalotaxine starting from readily available homopiperonyl alcohol achieved nine steps only two column chromatography purifications. Following tactical introduction Meinwald rearrangement, divergent syntheses (-)-cephalotine B an additional C3-O-C11 oxo-bridged bond (14 steps), (-)-fortuneicyclidin unprecedented C3-C10 its 2-epimer (16 steps) have also accomplished first time.

Язык: Английский

Процитировано

19
Electrochemical Trifluoromethylalkoxylation of Endocyclic Enamides in Batch and Flow DOI Creative Commons

Elise Leclercq,

Waël Barakat,

Radhouan Maazaoui

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(13), С. 2919 - 2925

Опубликована: Март 2, 2024

Abstract A regioselective electrochemical oxytrifluoromethylation of endocyclic enamides is reported. The 1,2‐difunctionalization proceeds under mild conditions and employs the inexpensive bench stable Langlois’ reagent. This multicomponent strategy gives access to a wide range α,β‐substituted amines by means various alcohols as nucleophiles in high yields with good functional group tolerance. In addition, an electrochemically induced C−H trifluoromethylation has been developed. continuous flow protocol using commercial microflow reactor was also developed improved reaction performance efficiency over traditional batch versions without any supporting electrolyte.

Язык: Английский

Процитировано

5
Enantioselective Synthesis of β-Aminoboronic Acids via Borylalkylation of Enamides DOI
Liguo Lu, Shuhan Chen, Weiyu Kong

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(24), С. 16639 - 16647

Опубликована: Июнь 10, 2024

Aminoboronic acids represent a class of significant compounds that have attracted attention in the fields drug discovery and organic synthesis. Despite notable progress their synthesis, efficient construction chiral β-aminoboronic with alkyl side chains remains challenging endeavor. Here, we introduce an unprecedented nickel-catalyzed asymmetric borylalkylation enamides, employing simple diamine ligand, readily available B2pin2, halides as coupling partners. This reaction serves platform for assembling diverse range acid derivatives flexible chains, displaying exceptional regio-, stereo-, enantioselectivities. Moreover, this transformation exhibits broad substrate scope remarkable tolerance toward various functional groups. Theoretical calculations demonstrate benzyl group on ligand is key to high enantiocontrol transformation. Additionally, exemplify practical application strategy through concise synthesis complex bioactive molecules.

Язык: Английский

Процитировано

5
Catalytic asymmetric synthesis of 1,2-diamines DOI Creative Commons
Francisco Foubelo, Carmén Nájera, María de Gracia Retamosa

и другие.

Chemical Society Reviews, Год журнала: 2024, Номер 53(15), С. 7983 - 8085

Опубликована: Янв. 1, 2024

The asymmetric catalytic synthesis of 1,2-diamines has received considerable interest, due to their presence in biologically active compounds and applications for the development synthetic building blocks, chiral ligands organocatalysts.

Язык: Английский

Процитировано

4
Water-Assisted Cascade Synthesis of Trifluoromethylated Dipyridodiazepinone Analogues: In vitro and In silico Antibacterial Studies DOI
Shivangi Jaiswal,

Dharma Kishore,

Annu Bhardwaj

и другие.

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(32), С. 6520 - 6531

Опубликована: Янв. 1, 2024

A water-assisted cascade reaction has been described to afford a new series of trifluoromethylated dipyridiodiazepinone derivatives as antibacterial agents. This methodology broad substrate scope with minimal waste generation.

Язык: Английский

Процитировано

4
Brønsted Acid-Catalyzed Diastereoselective Synthesis of Spiroisoindolinones from Enamides DOI
Miro Halaczkiewicz,

Arianit Maraj,

Harald Kelm

и другие.

Organic Letters, Год журнала: 2024, Номер 26(11), С. 2321 - 2325

Опубликована: Март 11, 2024

A highly diastereoselective synthesis of spiroisoindolinones from enamides and 3-hydroxy-isoindolinones is reported. The reaction proceeds rapidly in the presence p-toluenesulfonic acid as a Brønsted catalyst affords variety densely substituted with three contiguous stereogenic centers high yields (≤98%) diastereoselectivities (up to dr >98:<2:0:0).

Язык: Английский

Процитировано

3
Recent total synthesis of natural products leveraging a strategy of enamide cyclization DOI Creative Commons

C. Mi,

Jiayuan Zhai,

Xiao‐Ming Zhang

и другие.

Beilstein Journal of Organic Chemistry, Год журнала: 2025, Номер 21, С. 999 - 1009

Опубликована: Май 22, 2025

Enamides are distinctive amphiphilic synthons that can be strategically incorporated into cyclization reactions. The iminium species generated from enamides via nucleophilic addition or substitution capable of engaging in further electrophilic additions isomerization processes. Exploiting the multiple reactivities facilitates development diverse modes provide entries to various N -heterocycles, some which serve as key structural motifs natural alkaloids. This review highlights recent advancements enamide-based reactions, including enamide–alkyne cycloisomerization, [3 + 2] annulation, and polycyclization, with a particular emphasis on their pivotal role strategy total synthesis products.

Язык: Английский

Процитировано

0