Issue 20, 2024

Enantioselective synthesis of α-aryl α-hydrazino phosphonates

Abstract

Catalysts generated in situ by the combination of pyridine–hydrazone N,N-ligands and Pd(TFA)2 have been applied to the addition of arylboronic acids to formylphosphonate-derived hydrazones, yielding α-aryl α-hydrazino phosphonates in excellent enantioselectivities (96 → 99% ee). Subsequent removal of the benzyloxycarbonyl (Cbz) N-protecting group afforded key building blocks en route to appealing artificial peptides, herbicides and antitumoral derivatives. Experimental and computational data support a stereochemical model based on aryl-palladium intermediates in which the phosphono hydrazone coordinates in its Z-configuration, maximizing the interactions between the substrate and the pyridine–hydrazone ligand.

Graphical abstract: Enantioselective synthesis of α-aryl α-hydrazino phosphonates

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Article information

Article type
Edge Article
Submitted
02 Feb 2024
Accepted
22 Apr 2024
First published
23 Apr 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 7725-7731

Enantioselective synthesis of α-aryl α-hydrazino phosphonates

S. Alberca, J. Romero-Parra, I. Fernández, R. Fernández, J. M. Lassaletta and D. Monge, Chem. Sci., 2024, 15, 7725 DOI: 10.1039/D4SC00822G

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