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New Synthetic Routes to β‐Olefinic Trialkoxyphosphonium Salts and Phosphonates: Organometallic Variants of the Michaelis‐Arbuzov Reaction
Author(s) -
Hafner Andreas,
Von Philipsborn Wolfgang,
Salzer Albrecht
Publication year - 1986
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19860690733
Subject(s) - chemistry , phosphonium , wittig reaction , metal , group 2 organometallic chemistry , medicinal chemistry , nmr spectra database , reaction conditions , organic chemistry , stereochemistry , molecule , catalysis , spectral line , physics , astronomy
The low‐temperature addition of tertiary phosphites to [(allyl)Fe (CO) 4 ] + X − complexes proceeds regio‐ and stereospecifically and produces metal‐coordinated β‐olefinic trialkoxyphosphonium ions. These can be converted by various routes into the uncomplexed phosphonium salts or phosphonates. Similar reactions of acyclic [(dienyl)Fe(CO) 3 ] + X − compounds give metal‐coordinated (2,4‐dien‐1‐yl)trialkoxyphosphonium salts or dialkyl (2,4‐dien‐1‐yl)phosphonates. The mechanisms and their relationship to the classical Michaelis ‐ Arbuzov reaction are discussed. The new compounds are characterized, if possible, by 1 H‐, 13 C‐, and 31 P‐NMR spectra. The new phosphonium salts and phosphonates, potentially useful for Wittig ‐ Horner reactions, are difficult to obtain by conventional routes.