Round-Trip Oxidative Addition, Ligand Metathesis, and Reductive Elimination in a PIII/PV Synthetic Cycle

Round-Trip Oxidative Addition, Ligand Metathesis, and Reductive Elimination in a PIII/PV Synthetic Cycle

A synthetic cycle for aryl C–F substitution comprising oxidative addition, ligand metathesis, and reductive elimination at a C s -symmetric phosphorus triamide (1, P­{N­[o-NMe-C6H4]2}) is reported. Reaction of 1 with perfluoro­arenes (ArF–F) results in C–F oxidative addition, yielding fluoro­phospho...

Full description

Saved in:
Bibliographic Details
Published in:Journal of the American Chemical Society Vol. 142; no. 38; pp. 16188 - 16193
Main Authors: Lim, Soohyun, Radosevich, Alexander T
Format: Journal Article
Language:English
Japanese
Published: American Chemical Society 23-09-2020
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:A synthetic cycle for aryl C–F substitution comprising oxidative addition, ligand metathesis, and reductive elimination at a C s -symmetric phosphorus triamide (1, P­{N­[o-NMe-C6H4]2}) is reported. Reaction of 1 with perfluoro­arenes (ArF–F) results in C–F oxidative addition, yielding fluoro­phosphoranes 1·[F]­[ArF]. The P-fluoro substituent is exchanged for hydride by treatment with DIBAL-H, generating hydrido­phosphoranes 1·[H]­[ArF]. Heating of 1·[H]­[ArF] regenerates 1 by C–H reductive elimination of ArF–H, where experimental and computational studies establish a concerted but highly asynchronous mechanism. The results provide well-characterized examples of the full triad of elementary mechanistic aryl C–X substitution steps at a single main-group site.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.0c07580