New Ferrocenyl Phenol Thiophosphines

Abstract

Two new enantiomerically pure ferrocenyl phenol-thiophosphine compounds have been efficiently synthesized by a one pot procedure from enantiomerically pure alcohol (R)-(diphenylthiophosphinoferrocenyl)methanol 1 by a fully regioselective Friedel-Crafts reaction on phenols after strong acid activation. A mechanistic proposal through O-alkylation followed by rearrangement of the formed oxonium is proposed. All compounds have been and fully characterized by NMR(1H, 31P and 13C) and High Resolution Mass Spectroscopy. The molecular structure of one of these ferrocene derivatives have been determined by X ray diffraction analysis on monocrystal.

Reactivity of Planar‐Chiral α‐Ferrocenyl Carbocations towards Electron‐Rich Aromatics

“…First studies using phenols and anisole as arenes have recently been investigated , . The lower nucleophilicity of oxygen as compared to nitrogen increased the ability to undergo S E Ar reactions and hence o ‐( S p )‐ 8 was obtained in high yield (74 %, Scheme ).…”

“…Recently, the crystal structure of racemic o ‐ 8 has been reported . Therein, the phenyl moiety is positioned above the C 5 H 3 plane (–108.9°; herein 143.0(5) °) and the OH group is directed away from the P=S functionality, which results in the formation of hydrogen bridge bonds with the sulfur atoms of adjacent molecules, along the a ‐axis (Figure S8).…”