Direct Cyclopalladation of Fluorinated Benzyl Amines by Pd3(OAc)6: The Coexistence of Multinuclear Pdn Reaction Pathways Highlights the Importance of Pd Speciation in C–H Bond Activation

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F23%3A10475813" target="_blank" >RIV/00216208:11320/23:10475813 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216275:25310/23:39920567

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=kv5SHPep3C" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=kv5SHPep3C</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.organomet.3c00178" target="_blank" >10.1021/acs.organomet.3c00178</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Direct Cyclopalladation of Fluorinated Benzyl Amines by Pd3(OAc)6: The Coexistence of Multinuclear Pdn Reaction Pathways Highlights the Importance of Pd Speciation in C–H Bond Activation

Popis výsledku v původním jazyce

Palladacycles are key intermediates in catalytic C-H bond functionalization reactions and important precatalysts for cross-couplings.It is commonly believed that palladacycle formation occurs throughthe reaction of a substrate bearing a C-H bond ortho to a suitable metal-directing group for interaction with, typically,mononuclear &quot;Pd(OAc)(2)&quot; species, with cyclopalladationliberating acetic acid as the side product. In this study, we showthat N,N-dimethyl-fluoro-benzylamines, which can be cyclopalladated either ortho or para to fluorine affording two regioisomericproducts, can occur by a direct reaction of Pd3(OAc)(6), proceeding via higher-order cyclopalladated intermediates.Regioselectivity is altered subtly depending on the ratio of substrate:Pd3(OAc)(6) and the solvent used. Our findings are importantwhen considering mechanisms of Pd-mediated reactions involving theintermediacy of palladacycles, of particular relevance in catalyticC-H bond functionalization chemistry.

Název v anglickém jazyce

Direct Cyclopalladation of Fluorinated Benzyl Amines by Pd3(OAc)6: The Coexistence of Multinuclear Pdn Reaction Pathways Highlights the Importance of Pd Speciation in C–H Bond Activation

Popis výsledku anglicky

Palladacycles are key intermediates in catalytic C-H bond functionalization reactions and important precatalysts for cross-couplings.It is commonly believed that palladacycle formation occurs throughthe reaction of a substrate bearing a C-H bond ortho to a suitable metal-directing group for interaction with, typically,mononuclear &quot;Pd(OAc)(2)&quot; species, with cyclopalladationliberating acetic acid as the side product. In this study, we showthat N,N-dimethyl-fluoro-benzylamines, which can be cyclopalladated either ortho or para to fluorine affording two regioisomericproducts, can occur by a direct reaction of Pd3(OAc)(6), proceeding via higher-order cyclopalladated intermediates.Regioselectivity is altered subtly depending on the ratio of substrate:Pd3(OAc)(6) and the solvent used. Our findings are importantwhen considering mechanisms of Pd-mediated reactions involving theintermediacy of palladacycles, of particular relevance in catalyticC-H bond functionalization chemistry.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Organometallics

ISSN

0276-7333

e-ISSN

1520-6041

Svazek periodika

42

Číslo periodika v rámci svazku

16

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

2197-2205

Kód UT WoS článku

001011112000001

EID výsledku v databázi Scopus

2-s2.0-85163338041