Synergistic formal ring contraction for the enantioselective synthesis of spiropyrazolones

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F18%3A10378054" target="_blank" >RIV/00216208:11310/18:10378054 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1039/c8sc00913a" target="_blank" >https://doi.org/10.1039/c8sc00913a</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c8sc00913a" target="_blank" >10.1039/c8sc00913a</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Synergistic formal ring contraction for the enantioselective synthesis of spiropyrazolones

Popis výsledku v původním jazyce

The rapid generation of molecular complexity from simple reactants is a key challenge in organic synthesis. Spiro compounds, underrepresented 3D motifs in chemical libraries, represent a challenge due to the creation of spiro quaternary carbon and the need to control the 3D shape in one step. Herein, we report the first ring contraction/formal [6 + 2] cycloaddition using synergistic Pd(0)/secondary amine catalysis, obtaining [5,5]-spiropyrazolone derivatives in excellent yields and stereoselectivities. We demonstrate that this reaction has a broad scope of early and late stage derivatization that will benefit the creation of highly valuable chemical libraries using spiropyrazolone motifs. We detected the key palladium activated intermediate in its protonated form by mass spectrometry and characterized its structure by infrared spectroscopy and DFT calculations, allowing us to propose a conceivable mechanistic pathway for this reaction.

Název v anglickém jazyce

Synergistic formal ring contraction for the enantioselective synthesis of spiropyrazolones

Popis výsledku anglicky

The rapid generation of molecular complexity from simple reactants is a key challenge in organic synthesis. Spiro compounds, underrepresented 3D motifs in chemical libraries, represent a challenge due to the creation of spiro quaternary carbon and the need to control the 3D shape in one step. Herein, we report the first ring contraction/formal [6 + 2] cycloaddition using synergistic Pd(0)/secondary amine catalysis, obtaining [5,5]-spiropyrazolone derivatives in excellent yields and stereoselectivities. We demonstrate that this reaction has a broad scope of early and late stage derivatization that will benefit the creation of highly valuable chemical libraries using spiropyrazolone motifs. We detected the key palladium activated intermediate in its protonated form by mass spectrometry and characterized its structure by infrared spectroscopy and DFT calculations, allowing us to propose a conceivable mechanistic pathway for this reaction.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA18-20645S" target="_blank" >GA18-20645S: Kombinovaná katalýza organickými látkami a komplexy kovů (CORMECA)</a><br>

Návaznosti

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

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Chemical Science

ISSN

2041-6520

e-ISSN

—

Svazek periodika

9

Číslo periodika v rámci svazku

30

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

6

Strana od-do

6368-6373

Kód UT WoS článku

000441580100002

EID výsledku v databázi Scopus

2-s2.0-85051079060