A Kinetic Study of the Intramolecular Nitroaldol (Henry) Reaction Giving 2-Nitroindan-1-ols

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F19%3A39914400" target="_blank" >RIV/00216275:25310/19:39914400 - isvavai.cz</a>

Výsledek na webu

<a href="https://onlinelibrary.wiley.com/doi/abs/10.1002/slct.201900481" target="_blank" >https://onlinelibrary.wiley.com/doi/abs/10.1002/slct.201900481</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/slct.201900481" target="_blank" >10.1002/slct.201900481</a>

Jazyk výsledku

angličtina

Název v původním jazyce

A Kinetic Study of the Intramolecular Nitroaldol (Henry) Reaction Giving 2-Nitroindan-1-ols

Popis výsledku v původním jazyce

An intramolecular base-catalyzed nitroaldol reaction of three newly prepared 2-(2-nitroalkyl)benzaldehydes (1a-c) giving corresponding 2-nitroindan-1-ols (2a-c) was studied in water and five non-aqueous solvents. Whilst for the parent 2-(2-nitroethyl)benzaldehyde (1a) the reaction takes place in two kinetically discernible steps - deprotonation and cyclization, for 2-(2-nitropropyl)- and 2-(2-nitro-2-phenylethyl)benzaldehydes 1b and 1c general base-catalyzed formation of a reactive carbanion is rate-limitting. An unusually high Bronsted coefficient (beta(B)=1.12 +/- 0.03) was found for 1b indicating smaller imbalance of the transition state whose structure therefore resembles a nitronate. Cyclization products 2a-c prefer relative trans-configuration in ratios from 55:45 to 83:17 depending on the solvent. Mutual interconversion of the cis-/trans-diastereoisomers occurs either via nitronate species 2a(-) or via a reverse ring opening/ring closing pathway through the nitronate species 1b(-) and 1c(-). The mechanism was also supported by quantum calculations.

Název v anglickém jazyce

A Kinetic Study of the Intramolecular Nitroaldol (Henry) Reaction Giving 2-Nitroindan-1-ols

Popis výsledku anglicky

An intramolecular base-catalyzed nitroaldol reaction of three newly prepared 2-(2-nitroalkyl)benzaldehydes (1a-c) giving corresponding 2-nitroindan-1-ols (2a-c) was studied in water and five non-aqueous solvents. Whilst for the parent 2-(2-nitroethyl)benzaldehyde (1a) the reaction takes place in two kinetically discernible steps - deprotonation and cyclization, for 2-(2-nitropropyl)- and 2-(2-nitro-2-phenylethyl)benzaldehydes 1b and 1c general base-catalyzed formation of a reactive carbanion is rate-limitting. An unusually high Bronsted coefficient (beta(B)=1.12 +/- 0.03) was found for 1b indicating smaller imbalance of the transition state whose structure therefore resembles a nitronate. Cyclization products 2a-c prefer relative trans-configuration in ratios from 55:45 to 83:17 depending on the solvent. Mutual interconversion of the cis-/trans-diastereoisomers occurs either via nitronate species 2a(-) or via a reverse ring opening/ring closing pathway through the nitronate species 1b(-) and 1c(-). The mechanism was also supported by quantum calculations.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA17-08499S" target="_blank" >GA17-08499S: Recyklovatelné katalyzátory pro udržitelné technologie pokročilých organických intermediátů</a><br>

Návaznosti

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

Rok uplatnění

2019

Kód důvěrnosti údajů

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

Název periodika

ChemistrySelect

ISSN

2365-6549

e-ISSN

—

Svazek periodika

4

Číslo periodika v rámci svazku

13

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

7

Strana od-do

3973-3979

Kód UT WoS článku

000464282100049

EID výsledku v databázi Scopus

2-s2.0-85064093089