Reactivity of Ferrocenyl Phosphates Bearing (Hetero-)Aromatics and [3]Ferrocenophanes toward Anionic Phospho-Fries Rearrangements

Marcus Korb, Steve W. Lehrich, Heinrich Lang

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

The temperature-dependent behavior within anionic phospho-Fries rearrangements (apFr) of P(O)(OFc)(n),(EAr)(3-n) (Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4); E = O; Ar = phenyl, naphthyls, (R)-BINOL, [3]ferrocenophanyl; E = N, 1H-pyrrolyl, 1H-indolyl, 9H-carbazolyl; n = 1-3) is reported. While Fc undergoes one, the Ph-based apFr depends on temperature. First, the aryls are lithiated and rearranged, followed by Fc and N-heterocycles. Addition of Me2SO4 thus gave methylated Fc, contrary to non-organometallic aromatics giving mixtures of HO and MeO derivatives. The (R)-BINOL Fc phosphate gave Fc-rearranged phosphonate in 91% de. Exchanging O- with N-aliphatics prevented apFr, due to higher electron density at P. Also 1,2-N -> C migrations were observed. X-ray analysis confirms 1D H bridge bonds for OH and NH derivatives. The differences in reactivity between N-aliphatic and N-aromatic phosphoramidates were verified by electrochemistry. The redox potentials revealed lower values for the electron-rich aliphatics, showing no apFr, preventing a nucleophilic attack at P after lithiation. Redox separations for multiple Fc molecules are based on electrostatic interactions.

[GRAPHICS]

Original languageEnglish
Pages (from-to)3102-3124
Number of pages23
JournalJournal of Organic Chemistry
Volume82
Issue number6
DOIs
Publication statusPublished - 17 Mar 2017
Externally publishedYes

Cite this

@article{0234025bb0ca440e8bc1eec7560b64fb,
title = "Reactivity of Ferrocenyl Phosphates Bearing (Hetero-)Aromatics and [3]Ferrocenophanes toward Anionic Phospho-Fries Rearrangements",
abstract = "The temperature-dependent behavior within anionic phospho-Fries rearrangements (apFr) of P(O)(OFc)(n),(EAr)(3-n) (Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4); E = O; Ar = phenyl, naphthyls, (R)-BINOL, [3]ferrocenophanyl; E = N, 1H-pyrrolyl, 1H-indolyl, 9H-carbazolyl; n = 1-3) is reported. While Fc undergoes one, the Ph-based apFr depends on temperature. First, the aryls are lithiated and rearranged, followed by Fc and N-heterocycles. Addition of Me2SO4 thus gave methylated Fc, contrary to non-organometallic aromatics giving mixtures of HO and MeO derivatives. The (R)-BINOL Fc phosphate gave Fc-rearranged phosphonate in 91{\%} de. Exchanging O- with N-aliphatics prevented apFr, due to higher electron density at P. Also 1,2-N -> C migrations were observed. X-ray analysis confirms 1D H bridge bonds for OH and NH derivatives. The differences in reactivity between N-aliphatic and N-aromatic phosphoramidates were verified by electrochemistry. The redox potentials revealed lower values for the electron-rich aliphatics, showing no apFr, preventing a nucleophilic attack at P after lithiation. Redox separations for multiple Fc molecules are based on electrostatic interactions.[GRAPHICS]",
keywords = "METALATION-INDUCED REARRANGEMENT, ORTHO-DIRECTING GROUP, CRYSTAL-STRUCTURE, P-C, 1,3-CARBANIONIC REARRANGEMENTS, OXAZAPHOSPHOLIDINE-OXIDE, REGIOSELECTIVE SYNTHESIS, TERMINAL AZIRIDINES, NONAQUEOUS SOLVENTS, PALLADIUM COMPLEXES",
author = "Marcus Korb and Lehrich, {Steve W.} and Heinrich Lang",
year = "2017",
month = "3",
day = "17",
doi = "10.1021/acs.joc.7b00030",
language = "English",
volume = "82",
pages = "3102--3124",
journal = "The Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "6",

}

Reactivity of Ferrocenyl Phosphates Bearing (Hetero-)Aromatics and [3]Ferrocenophanes toward Anionic Phospho-Fries Rearrangements. / Korb, Marcus; Lehrich, Steve W.; Lang, Heinrich.

In: Journal of Organic Chemistry, Vol. 82, No. 6, 17.03.2017, p. 3102-3124.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Reactivity of Ferrocenyl Phosphates Bearing (Hetero-)Aromatics and [3]Ferrocenophanes toward Anionic Phospho-Fries Rearrangements

AU - Korb, Marcus

AU - Lehrich, Steve W.

AU - Lang, Heinrich

PY - 2017/3/17

Y1 - 2017/3/17

N2 - The temperature-dependent behavior within anionic phospho-Fries rearrangements (apFr) of P(O)(OFc)(n),(EAr)(3-n) (Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4); E = O; Ar = phenyl, naphthyls, (R)-BINOL, [3]ferrocenophanyl; E = N, 1H-pyrrolyl, 1H-indolyl, 9H-carbazolyl; n = 1-3) is reported. While Fc undergoes one, the Ph-based apFr depends on temperature. First, the aryls are lithiated and rearranged, followed by Fc and N-heterocycles. Addition of Me2SO4 thus gave methylated Fc, contrary to non-organometallic aromatics giving mixtures of HO and MeO derivatives. The (R)-BINOL Fc phosphate gave Fc-rearranged phosphonate in 91% de. Exchanging O- with N-aliphatics prevented apFr, due to higher electron density at P. Also 1,2-N -> C migrations were observed. X-ray analysis confirms 1D H bridge bonds for OH and NH derivatives. The differences in reactivity between N-aliphatic and N-aromatic phosphoramidates were verified by electrochemistry. The redox potentials revealed lower values for the electron-rich aliphatics, showing no apFr, preventing a nucleophilic attack at P after lithiation. Redox separations for multiple Fc molecules are based on electrostatic interactions.[GRAPHICS]

AB - The temperature-dependent behavior within anionic phospho-Fries rearrangements (apFr) of P(O)(OFc)(n),(EAr)(3-n) (Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4); E = O; Ar = phenyl, naphthyls, (R)-BINOL, [3]ferrocenophanyl; E = N, 1H-pyrrolyl, 1H-indolyl, 9H-carbazolyl; n = 1-3) is reported. While Fc undergoes one, the Ph-based apFr depends on temperature. First, the aryls are lithiated and rearranged, followed by Fc and N-heterocycles. Addition of Me2SO4 thus gave methylated Fc, contrary to non-organometallic aromatics giving mixtures of HO and MeO derivatives. The (R)-BINOL Fc phosphate gave Fc-rearranged phosphonate in 91% de. Exchanging O- with N-aliphatics prevented apFr, due to higher electron density at P. Also 1,2-N -> C migrations were observed. X-ray analysis confirms 1D H bridge bonds for OH and NH derivatives. The differences in reactivity between N-aliphatic and N-aromatic phosphoramidates were verified by electrochemistry. The redox potentials revealed lower values for the electron-rich aliphatics, showing no apFr, preventing a nucleophilic attack at P after lithiation. Redox separations for multiple Fc molecules are based on electrostatic interactions.[GRAPHICS]

KW - METALATION-INDUCED REARRANGEMENT

KW - ORTHO-DIRECTING GROUP

KW - CRYSTAL-STRUCTURE

KW - P-C

KW - 1,3-CARBANIONIC REARRANGEMENTS

KW - OXAZAPHOSPHOLIDINE-OXIDE

KW - REGIOSELECTIVE SYNTHESIS

KW - TERMINAL AZIRIDINES

KW - NONAQUEOUS SOLVENTS

KW - PALLADIUM COMPLEXES

U2 - 10.1021/acs.joc.7b00030

DO - 10.1021/acs.joc.7b00030

M3 - Article

VL - 82

SP - 3102

EP - 3124

JO - The Journal of Organic Chemistry

JF - The Journal of Organic Chemistry

SN - 0022-3263

IS - 6

ER -