Synthesis and ligand properties of 1-phosphaethenyl-2-phosphanylferrocenes

Ryo Takita; Yuko Takada; Rader S. Jensen; Masaaki Okazaki; Fumiyuki Ozawa

doi:10.1021/om8008316

Synthesis and ligand properties of 1-phosphaethenyl-2-phosphanylferrocenes

Ryo Takita, Yuko Takada, Rader S. Jensen, Masaaki Okazaki, Fumiyuki Ozawa^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

21 Citations (Scopus)

Abstract

(S)-1-Phosphaemenyl-2-diarylphosphanylferrocenes with planar chirality (Fc(CH=PMes*)PAr₂: PAr₂ = PPh₂ (3a), P(1-naphmyl)Ph (3b)) are prepared in high yields from optically active 2-phosphanylferrocenecarboxaldehydes by the phospha-Peterson reactions with Mes*P(Li)SiMe₃ in THF. The stereo-chemistry of 3b is determined by X-ray diffraction analysis. Compounds 3a and 3b readily react with [PtMe₂(μ-SMe₂)]₂ in Et₂O to afford dimethyl complexes with bidentate coordination of these ligands (PtMe₂(L): L = 3a (4a), 3b (4b)). The X-ray structure of 4b reveals almost identical trans-influence of the phosphaethenyl and phosphanyl groups, snowing comparable cr-donating abilities of those components. Treatment of 3a and 3b with [Pd(η³-allyl)(μ-Cl)]₂ in CH ₂Cl₂ in the presence of AgOTf forms the corresponding π-allyl complexes [Pd(η³-allyl)(L)]OTf (L = 3a (5a), 3b (5b)), respectively, which are mixtures of diastereomers with endo- and exo-oriented π-allyl ligands. Complex 5a catalyzes hydroamination of 1,3-cyclohexadiene with aniline in toluene in the presence of 5 A molecular sieves at room temperature, giving N-cyclohexen-3-ylaniline in 84% yield.

Original language	English
Pages (from-to)	6279-6285
Number of pages	7
Journal	Organometallics
Volume	27
Issue number	23
DOIs	https://doi.org/10.1021/om8008316
Publication status	Published - 2008 Dec 8

ASJC Scopus subject areas

Organic Chemistry
Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Synthesis and ligand properties of 1-phosphaethenyl-2-phosphanylferrocenes",

abstract = "(S)-1-Phosphaemenyl-2-diarylphosphanylferrocenes with planar chirality (Fc(CH=PMes*)PAr2: PAr2 = PPh2 (3a), P(1-naphmyl)Ph (3b)) are prepared in high yields from optically active 2-phosphanylferrocenecarboxaldehydes by the phospha-Peterson reactions with Mes*P(Li)SiMe3 in THF. The stereo-chemistry of 3b is determined by X-ray diffraction analysis. Compounds 3a and 3b readily react with [PtMe2(μ-SMe2)]2 in Et2O to afford dimethyl complexes with bidentate coordination of these ligands (PtMe2(L): L = 3a (4a), 3b (4b)). The X-ray structure of 4b reveals almost identical trans-influence of the phosphaethenyl and phosphanyl groups, snowing comparable cr-donating abilities of those components. Treatment of 3a and 3b with [Pd(η3-allyl)(μ-Cl)]2 in CH 2Cl2 in the presence of AgOTf forms the corresponding π-allyl complexes [Pd(η3-allyl)(L)]OTf (L = 3a (5a), 3b (5b)), respectively, which are mixtures of diastereomers with endo- and exo-oriented π-allyl ligands. Complex 5a catalyzes hydroamination of 1,3-cyclohexadiene with aniline in toluene in the presence of 5 A molecular sieves at room temperature, giving N-cyclohexen-3-ylaniline in 84% yield.",

author = "Ryo Takita and Yuko Takada and Jensen, {Rader S.} and Masaaki Okazaki and Fumiyuki Ozawa",

year = "2008",

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T1 - Synthesis and ligand properties of 1-phosphaethenyl-2-phosphanylferrocenes

AU - Takita, Ryo

AU - Takada, Yuko

AU - Jensen, Rader S.

AU - Okazaki, Masaaki

AU - Ozawa, Fumiyuki

PY - 2008/12/8

Y1 - 2008/12/8

N2 - (S)-1-Phosphaemenyl-2-diarylphosphanylferrocenes with planar chirality (Fc(CH=PMes*)PAr2: PAr2 = PPh2 (3a), P(1-naphmyl)Ph (3b)) are prepared in high yields from optically active 2-phosphanylferrocenecarboxaldehydes by the phospha-Peterson reactions with Mes*P(Li)SiMe3 in THF. The stereo-chemistry of 3b is determined by X-ray diffraction analysis. Compounds 3a and 3b readily react with [PtMe2(μ-SMe2)]2 in Et2O to afford dimethyl complexes with bidentate coordination of these ligands (PtMe2(L): L = 3a (4a), 3b (4b)). The X-ray structure of 4b reveals almost identical trans-influence of the phosphaethenyl and phosphanyl groups, snowing comparable cr-donating abilities of those components. Treatment of 3a and 3b with [Pd(η3-allyl)(μ-Cl)]2 in CH 2Cl2 in the presence of AgOTf forms the corresponding π-allyl complexes [Pd(η3-allyl)(L)]OTf (L = 3a (5a), 3b (5b)), respectively, which are mixtures of diastereomers with endo- and exo-oriented π-allyl ligands. Complex 5a catalyzes hydroamination of 1,3-cyclohexadiene with aniline in toluene in the presence of 5 A molecular sieves at room temperature, giving N-cyclohexen-3-ylaniline in 84% yield.

AB - (S)-1-Phosphaemenyl-2-diarylphosphanylferrocenes with planar chirality (Fc(CH=PMes*)PAr2: PAr2 = PPh2 (3a), P(1-naphmyl)Ph (3b)) are prepared in high yields from optically active 2-phosphanylferrocenecarboxaldehydes by the phospha-Peterson reactions with Mes*P(Li)SiMe3 in THF. The stereo-chemistry of 3b is determined by X-ray diffraction analysis. Compounds 3a and 3b readily react with [PtMe2(μ-SMe2)]2 in Et2O to afford dimethyl complexes with bidentate coordination of these ligands (PtMe2(L): L = 3a (4a), 3b (4b)). The X-ray structure of 4b reveals almost identical trans-influence of the phosphaethenyl and phosphanyl groups, snowing comparable cr-donating abilities of those components. Treatment of 3a and 3b with [Pd(η3-allyl)(μ-Cl)]2 in CH 2Cl2 in the presence of AgOTf forms the corresponding π-allyl complexes [Pd(η3-allyl)(L)]OTf (L = 3a (5a), 3b (5b)), respectively, which are mixtures of diastereomers with endo- and exo-oriented π-allyl ligands. Complex 5a catalyzes hydroamination of 1,3-cyclohexadiene with aniline in toluene in the presence of 5 A molecular sieves at room temperature, giving N-cyclohexen-3-ylaniline in 84% yield.

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ER -

Synthesis and ligand properties of 1-phosphaethenyl-2-phosphanylferrocenes

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