Synthetic studies for the 1,3-iterative organoiron approach to the synthesis of siculinine: efficient arylation using a diarylcuprate reagent

George Stephenson; Ian M. Palotai; Sarah Thomas; Michael Tinkl

doi:10.1002/ejoc.201201056

Synthetic studies for the 1,3-iterative organoiron approach to the synthesis of siculinine: efficient arylation using a diarylcuprate reagent

George Stephenson
, Ian M. Palotai
, Sarah Thomas
, Michael Tinkl

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

2 Citations (Scopus)

18 Downloads (Pure)

Abstract

Disubstituted (cyclohexadienyl)iron(1+) complex 2b is prepared by an improved route that starts from 1,2-dimethoxycyclohexa-1,4-diene 3. In five steps, the synthesis of 2b is achieved by complexation with Fe(CO)5, hydride abstraction,
hydrolysis, addition of EtO2CCH2ZrBr, and reaction with HBF4. In the presence of dimethyl sulfide, the reaction of 2b with 2-[CH2N(CH2CH=CH2)2]-functionalized diarylcuprate reagent 7 gave the 5α-arylcyclohexadiene complex 1b in 88% yield. A DFT study compared diarylzinc and diarylcuprate reagents containing chelating CH2NMe2 substituents.

Original language	English
Pages (from-to)	1895–1901
Number of pages	7
Journal	European Journal of Organic Chemistry
Volume	2013
Issue number	10
Early online date	18 Feb 2013
DOIs	https://doi.org/10.1002/ejoc.201201056
Publication status	Published - Apr 2013

Keywords

Synthesis design
Arylation
C–C coupling
Alkaloids
Regioselectivity
Iron
Copper
Density functional calculations

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10.1002/ejoc.201201056

Stephenson_201201056_Full-Paper_EurJOC_2013_1895–1901Accepted author manuscript, 3.5 MB

2 Citations
1 Article

Stereomanipulation of (η5-1-arylcyclohexadienyl)iron complexes
Anson, C. E., Malkov, A. V., Roe, C., Sandoe, E. J. & Stephenson, G. R., Jan 2008, In: European Journal of Organic Chemistry. 2008, 1, p. 196-213 18 p.
Research output: Contribution to journal › Article › peer-review

15 Citations (Scopus)

Cite this

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title = "Synthetic studies for the 1,3-iterative organoiron approach to the synthesis of siculinine: efficient arylation using a diarylcuprate reagent",

abstract = "Disubstituted (cyclohexadienyl)iron(1+) complex 2b is prepared by an improved route that starts from 1,2-dimethoxycyclohexa-1,4-diene 3. In five steps, the synthesis of 2b is achieved by complexation with Fe(CO)5, hydride abstraction, hydrolysis, addition of EtO2CCH2ZrBr, and reaction with HBF4. In the presence of dimethyl sulfide, the reaction of 2b with 2-[CH2N(CH2CH=CH2)2]-functionalized diarylcuprate reagent 7 gave the 5α-arylcyclohexadiene complex 1b in 88\% yield. A DFT study compared diarylzinc and diarylcuprate reagents containing chelating CH2NMe2 substituents.",

keywords = "Synthesis design , Arylation, C–C coupling, Alkaloids, Regioselectivity, Iron, Copper, Density functional calculations",

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T1 - Synthetic studies for the 1,3-iterative organoiron approach to the synthesis of siculinine: efficient arylation using a diarylcuprate reagent

AU - Stephenson, George

AU - Palotai, Ian M.

AU - Thomas, Sarah

AU - Tinkl, Michael

PY - 2013/4

Y1 - 2013/4

N2 - Disubstituted (cyclohexadienyl)iron(1+) complex 2b is prepared by an improved route that starts from 1,2-dimethoxycyclohexa-1,4-diene 3. In five steps, the synthesis of 2b is achieved by complexation with Fe(CO)5, hydride abstraction, hydrolysis, addition of EtO2CCH2ZrBr, and reaction with HBF4. In the presence of dimethyl sulfide, the reaction of 2b with 2-[CH2N(CH2CH=CH2)2]-functionalized diarylcuprate reagent 7 gave the 5α-arylcyclohexadiene complex 1b in 88% yield. A DFT study compared diarylzinc and diarylcuprate reagents containing chelating CH2NMe2 substituents.

AB - Disubstituted (cyclohexadienyl)iron(1+) complex 2b is prepared by an improved route that starts from 1,2-dimethoxycyclohexa-1,4-diene 3. In five steps, the synthesis of 2b is achieved by complexation with Fe(CO)5, hydride abstraction, hydrolysis, addition of EtO2CCH2ZrBr, and reaction with HBF4. In the presence of dimethyl sulfide, the reaction of 2b with 2-[CH2N(CH2CH=CH2)2]-functionalized diarylcuprate reagent 7 gave the 5α-arylcyclohexadiene complex 1b in 88% yield. A DFT study compared diarylzinc and diarylcuprate reagents containing chelating CH2NMe2 substituents.

KW - Synthesis design

KW - Arylation

KW - C–C coupling

KW - Alkaloids

KW - Regioselectivity

KW - Iron

KW - Copper

KW - Density functional calculations

U2 - 10.1002/ejoc.201201056

DO - 10.1002/ejoc.201201056

M3 - Article

SN - 1434-193X

VL - 2013

SP - 1895

EP - 1901

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 10

ER -

Synthetic studies for the 1,3-iterative organoiron approach to the synthesis of siculinine: efficient arylation using a diarylcuprate reagent

Abstract

Keywords

Access to Document

Research output

Stereomanipulation of (η5-1-arylcyclohexadienyl)iron complexes

Cite this