Palladium-catalyzed reaction of 2-iodoferrocenyl alcohols with internal alkynes: Synthesis of functionally 1,2-disubstituted ferrocenes and ferroceno-pyrans

Baris Yucel; Bahar Sanli; Huseyin Soylemez; Huseyin Akbulut

doi:10.1016/j.jorganchem.2012.01.007

Palladium-catalyzed reaction of 2-iodoferrocenyl alcohols with internal alkynes: Synthesis of functionally 1,2-disubstituted ferrocenes and ferroceno-pyrans

Baris Yucel^*, Bahar Sanli, Huseyin Soylemez, Huseyin Akbulut

^*Corresponding author for this work

Department of Chemistry

Istanbul Technical University

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

9 Citations (Scopus)

Abstract

The reaction of racemic (2-iodoferrocenyl)methanol with internal alkynes in the presence of (dppf)PdCl ₂ and i-Pr ₂NH produces alkenyl-substituted ferrocene carboxaldehydes in moderate yields. All reactions are carried out at 100 or 120 °C for different reaction times (between 6 and 26 h) in a screw-cap Pyrex bottle. The scope and limitations of this reaction are studied by employing variously substituted 11 internal alkynes. The reactions are regioselective with alkynes having a sterically crowded substituent such as t-butyl and trimethylsilyl groups. Moreover, racemic 1-(2-iodoferrocenyl)ethanol derivatives are synthesized as two diastereomers. Both diastereomers are reacted with internal alkynes in the presence of (dppf)PdCl ₂ and i-Pr ₂NH at 120 °C to afford alkenyl-substituted acetylferrocenes and ferroceno-pyrans in moderate to good yields. According to the alkyne employed, different reaction times (between 6 and 55 h) are necessary to drive the reactions to completion. Mechanisms are also suggested for the formation of observed products.

Original language	English
Pages (from-to)	49-64
Number of pages	16
Journal	Journal of Organometallic Chemistry
Volume	704
DOIs	https://doi.org/10.1016/j.jorganchem.2012.01.007
Publication status	Published - 1 May 2012

Funding

The authors thank the Scientific and Technical Research Council of Turkey ( TBAG-107T811 ), the Research Board of Istanbul Technical University ( BAP-32464 and BAP-34044 ) for financial support of this research. The authors are particularly grateful to Professor Dr. Süheyla Özbey, Hacettepe University, Department of Physics Engineering, for the X-ray crystal structure analysis of compound 7a .

Funders	Funder number
Türkiye Bilimsel ve Teknolojik Araştirma Kurumu	TBAG-107T811
Istanbul Teknik Üniversitesi	BAP-32464, BAP-34044

Keywords

1,2-Disubstituted ferrocene
Ferrocene carboxaldehyde
Ferroceno-pyran ferrocenyl alcohol
Ferrocenyl alkene

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10.1016/j.jorganchem.2012.01.007

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@article{c3ee3f0a2f504134abb1968276ba4c9e,

title = "Palladium-catalyzed reaction of 2-iodoferrocenyl alcohols with internal alkynes: Synthesis of functionally 1,2-disubstituted ferrocenes and ferroceno-pyrans",

abstract = "The reaction of racemic (2-iodoferrocenyl)methanol with internal alkynes in the presence of (dppf)PdCl 2 and i-Pr 2NH produces alkenyl-substituted ferrocene carboxaldehydes in moderate yields. All reactions are carried out at 100 or 120 °C for different reaction times (between 6 and 26 h) in a screw-cap Pyrex bottle. The scope and limitations of this reaction are studied by employing variously substituted 11 internal alkynes. The reactions are regioselective with alkynes having a sterically crowded substituent such as t-butyl and trimethylsilyl groups. Moreover, racemic 1-(2-iodoferrocenyl)ethanol derivatives are synthesized as two diastereomers. Both diastereomers are reacted with internal alkynes in the presence of (dppf)PdCl 2 and i-Pr 2NH at 120 °C to afford alkenyl-substituted acetylferrocenes and ferroceno-pyrans in moderate to good yields. According to the alkyne employed, different reaction times (between 6 and 55 h) are necessary to drive the reactions to completion. Mechanisms are also suggested for the formation of observed products.",

keywords = "1,2-Disubstituted ferrocene, Ferrocene carboxaldehyde, Ferroceno-pyran ferrocenyl alcohol, Ferrocenyl alkene",

author = "Baris Yucel and Bahar Sanli and Huseyin Soylemez and Huseyin Akbulut",

year = "2012",

month = may,

day = "1",

doi = "10.1016/j.jorganchem.2012.01.007",

language = "English",

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journal = "Journal of Organometallic Chemistry",

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T1 - Palladium-catalyzed reaction of 2-iodoferrocenyl alcohols with internal alkynes

T2 - Synthesis of functionally 1,2-disubstituted ferrocenes and ferroceno-pyrans

AU - Yucel, Baris

AU - Sanli, Bahar

AU - Soylemez, Huseyin

AU - Akbulut, Huseyin

PY - 2012/5/1

Y1 - 2012/5/1

N2 - The reaction of racemic (2-iodoferrocenyl)methanol with internal alkynes in the presence of (dppf)PdCl 2 and i-Pr 2NH produces alkenyl-substituted ferrocene carboxaldehydes in moderate yields. All reactions are carried out at 100 or 120 °C for different reaction times (between 6 and 26 h) in a screw-cap Pyrex bottle. The scope and limitations of this reaction are studied by employing variously substituted 11 internal alkynes. The reactions are regioselective with alkynes having a sterically crowded substituent such as t-butyl and trimethylsilyl groups. Moreover, racemic 1-(2-iodoferrocenyl)ethanol derivatives are synthesized as two diastereomers. Both diastereomers are reacted with internal alkynes in the presence of (dppf)PdCl 2 and i-Pr 2NH at 120 °C to afford alkenyl-substituted acetylferrocenes and ferroceno-pyrans in moderate to good yields. According to the alkyne employed, different reaction times (between 6 and 55 h) are necessary to drive the reactions to completion. Mechanisms are also suggested for the formation of observed products.

AB - The reaction of racemic (2-iodoferrocenyl)methanol with internal alkynes in the presence of (dppf)PdCl 2 and i-Pr 2NH produces alkenyl-substituted ferrocene carboxaldehydes in moderate yields. All reactions are carried out at 100 or 120 °C for different reaction times (between 6 and 26 h) in a screw-cap Pyrex bottle. The scope and limitations of this reaction are studied by employing variously substituted 11 internal alkynes. The reactions are regioselective with alkynes having a sterically crowded substituent such as t-butyl and trimethylsilyl groups. Moreover, racemic 1-(2-iodoferrocenyl)ethanol derivatives are synthesized as two diastereomers. Both diastereomers are reacted with internal alkynes in the presence of (dppf)PdCl 2 and i-Pr 2NH at 120 °C to afford alkenyl-substituted acetylferrocenes and ferroceno-pyrans in moderate to good yields. According to the alkyne employed, different reaction times (between 6 and 55 h) are necessary to drive the reactions to completion. Mechanisms are also suggested for the formation of observed products.

KW - 1,2-Disubstituted ferrocene

KW - Ferrocene carboxaldehyde

KW - Ferroceno-pyran ferrocenyl alcohol

KW - Ferrocenyl alkene

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DO - 10.1016/j.jorganchem.2012.01.007

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SN - 0022-328X

VL - 704

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JF - Journal of Organometallic Chemistry

ER -

Palladium-catalyzed reaction of 2-iodoferrocenyl alcohols with internal alkynes: Synthesis of functionally 1,2-disubstituted ferrocenes and ferroceno-pyrans

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