Haloalkenyl Imidoyl Halides as Multifacial Substrates in the Stereoselective Synthesis of N-Alkenyl Compounds

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F21%3A00541416" target="_blank" >RIV/61388963:_____/21:00541416 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/21:10439265

Výsledek na webu

<a href="https://doi.org/10.1002/adsc.202100009" target="_blank" >https://doi.org/10.1002/adsc.202100009</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/adsc.202100009" target="_blank" >10.1002/adsc.202100009</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Haloalkenyl Imidoyl Halides as Multifacial Substrates in the Stereoselective Synthesis of N-Alkenyl Compounds

Popis výsledku v původním jazyce

N-Alkenyl compounds are versatile synthetic building blocks and their stereoselective transformations are key processes in the synthesis of many prominent classes of natural products, pharmaceuticals, and agrochemicals. However, a large structural variety of known N-alkenyl compounds and their diverse reactivity have so far precluded the development of a general method for their stereoselective synthesis. Herein we present an aluminum halide-mediated, highly stereoselective, efficient and scalable transformation of commercially available N-fluoroalkyl-1,2,3-triazoles to N-haloalkenyl imidoyl halides, and demonstrate their use in the synthesis of stereodefined N-alkenyl amides, amidines, imines, hydrazonoamides, imidothioates, iminophosphonates, 1,2,4-triazoles and tetrazoles. The reaction is of wide scope on both the triazole substrate and aluminum halide, providing highly functionalized products. Mechanistic and computational investigations suggest a reaction mechanism involving the triazole ring opening, initiated by the coordination of nitrogen one of the triazole ring to the Lewis acid, N2 elimination and the formation of a vinyl cation intermediate, which reacts with nitrogen-bound aluminum halide, followed by a series of halide exchange reactions on C−X and Al−X bonds. (Figure presented.).

Název v anglickém jazyce

Haloalkenyl Imidoyl Halides as Multifacial Substrates in the Stereoselective Synthesis of N-Alkenyl Compounds

Popis výsledku anglicky

N-Alkenyl compounds are versatile synthetic building blocks and their stereoselective transformations are key processes in the synthesis of many prominent classes of natural products, pharmaceuticals, and agrochemicals. However, a large structural variety of known N-alkenyl compounds and their diverse reactivity have so far precluded the development of a general method for their stereoselective synthesis. Herein we present an aluminum halide-mediated, highly stereoselective, efficient and scalable transformation of commercially available N-fluoroalkyl-1,2,3-triazoles to N-haloalkenyl imidoyl halides, and demonstrate their use in the synthesis of stereodefined N-alkenyl amides, amidines, imines, hydrazonoamides, imidothioates, iminophosphonates, 1,2,4-triazoles and tetrazoles. The reaction is of wide scope on both the triazole substrate and aluminum halide, providing highly functionalized products. Mechanistic and computational investigations suggest a reaction mechanism involving the triazole ring opening, initiated by the coordination of nitrogen one of the triazole ring to the Lewis acid, N2 elimination and the formation of a vinyl cation intermediate, which reacts with nitrogen-bound aluminum halide, followed by a series of halide exchange reactions on C−X and Al−X bonds. (Figure presented.).

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/LTAUSA18037" target="_blank" >LTAUSA18037: Syntéza a reaktivita N-fluoralkylovaných sloučenin</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2021

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Advanced Synthesis & Catalysis

ISSN

1615-4150

e-ISSN

1615-4169

Svazek periodika

363

Číslo periodika v rámci svazku

13

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

9

Strana od-do

3258-3266

Kód UT WoS článku

000625420400001

EID výsledku v databázi Scopus

2-s2.0-85101981506