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The Chemistry of Diene–Iron and Dienyl–Iron Complexes

Organoiron Compounds (2013)

  1. Ingmar Bauer,
  2. Hans-Joachim Knölker

Published Online: 18 MAR 2013

DOI: 10.1002/9780470682531.pat0652

Patai's Chemistry of Functional Groups

Patai's Chemistry of Functional Groups

How to Cite

Bauer, I. and Knölker, H.-J. 2013. The Chemistry of Diene–Iron and Dienyl–Iron Complexes. Patai's Chemistry of Functional Groups. .

Author Information

  1. Department Chemie, Technische Universität Dresden, Bergstraße 66, 01069 Dresden, Germany Fax: +49 351-463-37030; e-mail: hans-joachim.knoelker@tu-dresden.de

Publication History

  1. Published Online: 18 MAR 2013

Chemistry Terms

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Abstract

4-Diene)iron complexes and η5-dienyliumiron complex salts represent intriguing structures with planar π-donating C4 or C5 ligands attached to the central iron atom. In many cases, they are rather stable compounds due to an 18-electron count at the iron center. Tricarbonyl(η4-diene)iron complexes are formed from cyclic and acylic 1,3-dienes and a tricarbonyliron source. Under certain conditions 1,4-dienes can be employed with concomitant rearragement of the double bonds. The tricarbonyliron source can be a binary carbonyliron complex or a tricarbonyliron transfer reagent. (η4-1-Azabutadiene)tricarbonyliron complexes have been proven to transfer the tricarbonyliron unit efficiently to the diene system. 1-Azabutadiene ligands can even be employed in catalytic amounts. Chiral 1-azabutadiene ligands enable the catalytic asymmetric synthesis of planar chiral (η4-diene)iron complexes. The tricarbonyliron fragment in (η4-diene)iron complexes is shielding one side of the diene system. Thus, it can be utilized to control stereoselective reactions in its proximity. Moreover, due to their stability (η4-diene)iron complexes can be employed as protected 1,3-dienes. η5-Dienyliumiron complexes are generated from (η4-diene)iron complexes by two principal methods. Either by hydride abstraction at the α-position of the diene ligand using triphenylcarbenium salts or by elimination of leaving groups adjacent to the diene system. η5-Dienyliumiron complexes are versatile electrophiles which react with a large variety of nucleophiles leading to functionalized (η4-diene)iron complexes. In most cases, nucleophilic attack at the terminus of the co-ordinated dienylium system is preferred. Especially with C-nucleophiles, the reaction is extremely useful for the construction of natural products or advanced synthetic precursors. Employment of substituted anilines as nucleophiles has paved the way to the total synthesis of a large number of biologically active carbazole alkaloids. After exploiting the activating, protecting or stereodirecting effect of the iron complex, the organic ligand is disengaged from the metal. A variety of mild demetalation procedures has been developed for this purpose.

In addition to the stoichiometric reactions, first examples of catalytic applications of (diene)iron complexes are dicussed in this chapter.

Keywords:

  • alkaloids;
  • catalysis;
  • complexation;
  • demetalation;
  • dienes;
  • iron;
  • natural products;
  • oxidative cyclization;
  • spirocyclization;
  • stereoselective synthesis

Featured Compounds

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  1. 1 - 47
Compound 1
Molecular Weight:237.2964
Molecular Formula:C16H15NO
InChIKey:MBPYUPPKESSJGW-WUSSVBECSA-N
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Compound 2
Molecular Weight:236.2885
Molecular Formula:Not Available
InChIKey:Not Available
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Compound R-3a
Molecular Weight:235.3236
Molecular Formula:C17H17N
InChIKey:JGCKWLXPTFJZOZ-XTJUUECFSA-N
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Compound S-3a
Molecular Weight:235.3236
Molecular Formula:C17H17N
InChIKey:JGCKWLXPTFJZOZ-OWRPESROSA-N
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Compound 3b
Molecular Weight:245.3169
Molecular Formula:C15H19NO2
InChIKey:HBGBBLZKTKTRTP-DSQIVDPBSA-N
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Compound 3c
Molecular Weight:259.3434
Molecular Formula:C16H21NO2
InChIKey:HGIXXCPGVIWYQA-QQKRKUKPSA-N
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Compound 3d
Molecular Weight:629.7807
Molecular Formula:C35H51NO9
InChIKey:XFFGWWYGYGHGKR-FGOFNCGVSA-N
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Compound 3e
Molecular Weight:413.5097
Molecular Formula:C30H23NO
InChIKey:UWQNAUKIBQRCSO-WAEKEDHUSA-N
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Compound 3f
Molecular Weight:441.5629
Molecular Formula:C32H27NO
InChIKey:ISLQONCZAYTTFI-VIBIKFALSA-N
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Compound 3g
Molecular Weight:255.3547
Molecular Formula:C17H21NO
InChIKey:WTERIOFWRCETPI-GDXANTJSSA-N
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Compound 3h
Molecular Weight:255.3547
Molecular Formula:C17H21NO
InChIKey:WQCZVBSRWMWPCL-UQVNSJMISA-N
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Compound 3j
Molecular Weight:361.4767
Molecular Formula:C24H27NO2
InChIKey:IOSUFFMUNPCXCH-AYKCNIJDSA-N
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Compound 3k
Molecular Weight:507.6625
Molecular Formula:C34H37NO3
InChIKey:YDSMVXLRYOVTLM-PUIHNHHCSA-N
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Compound R-3i
Molecular Weight:375.5033
Molecular Formula:C25H29NO2
InChIKey:GYPFNRPVYUHEPR-LUUKBKGVSA-N
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Compound 4
Molecular Weight:281.129
Molecular Formula:C12H19FeNO3
InChIKey:ANTNKCFTWMIOED-YWEMJPMZSA-N
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Compound 5
Molecular Weight:553.499
Molecular Formula:C24H39FeNO8Si
InChIKey:LJHLPFMTJDNFPP-WRUBNFPBSA-N
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Compound 6
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 12
Molecular Weight:436.022
Molecular Formula:C12H11F6FeO5P
InChIKey:NPCCXIADNJUXBV-UHFFFAOYSA-N
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Compound 15
Molecular Weight:436.022
Molecular Formula:C12H11F6FeO5P
InChIKey:BILHMQSAWMARPQ-UHFFFAOYSA-N
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Compound 13
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 16
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 14
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 17
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 13a
Molecular Weight:292.066
Molecular Formula:C12H12FeO5
InChIKey:UEFVWHFEJIKFHE-UHFFFAOYSA-N
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Compound 13b
Molecular Weight:317.075
Molecular Formula:C13H11FeNO5
InChIKey:FHFVWEVSXULRQM-XWCOYVICSA-N
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Compound 13c
Molecular Weight:306.092
Molecular Formula:C13H14FeO5
InChIKey:YNUDOGCSCVTCSJ-XWCOYVICSA-N
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Compound 13d
Molecular Weight:400.227
Molecular Formula:C18H16FeO5S
InChIKey:LNZDHGVFDVMKIP-WGVOJFRMSA-N
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Compound 13e
Molecular Weight:308.065
Molecular Formula:C12H12FeO6
InChIKey:UXRNSSIFEDTWIT-XWCOYVICSA-N
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Compound 13f
Molecular Weight:422.164
Molecular Formula:C17H18FeO9
InChIKey:ROUXJAAEBXGRCY-RASHCQHBSA-N
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Compound 14a
Molecular Weight:293.074
Molecular Formula:C12H13FeO5
InChIKey:JVGZUYNTMAWHQB-UHFFFAOYSA-N
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Compound 14b
Molecular Weight:318.083
Molecular Formula:C13H12FeNO5
InChIKey:BPFQMARLIFKTIT-WNHJFKIESA-N
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Compound 14c
Molecular Weight:307.1
Molecular Formula:C13H15FeO5
InChIKey:JDQWTLLBUMZJLQ-XJGUQWRXSA-N
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Compound 14d
Molecular Weight:401.235
Molecular Formula:C18H17FeO5S
InChIKey:ZBOJAZWOWSNBFN-DLSZIHIJSA-N
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Compound 14e
Molecular Weight:309.073
Molecular Formula:C12H13FeO6
InChIKey:JHWWINCSZXXWBL-FPVLLIHKSA-N
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Compound 14f
Molecular Weight:423.172
Molecular Formula:C17H19FeO9
InChIKey:KJJRZTBQAJFADM-VQTXXYAFSA-N
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Compound 16a
Molecular Weight:292.066
Molecular Formula:C12H12FeO5
InChIKey:APSYXZDXSWQORM-UHFFFAOYSA-N
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Compound 16b
Molecular Weight:317.075
Molecular Formula:C13H11FeNO5
InChIKey:ANYWYYFCRBNVKA-USHJOAKVSA-N
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Compound 16c
Molecular Weight:306.092
Molecular Formula:C13H14FeO5
InChIKey:OOLPRDXEUAIJDX-USHJOAKVSA-N
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Compound 16d
Molecular Weight:400.227
Molecular Formula:C18H16FeO5S
InChIKey:HQNPHNQZNBKAGS-XCYGSCDUSA-N
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Compound 16e
Molecular Weight:308.065
Molecular Formula:C12H12FeO6
InChIKey:NBYAYVGEYFMJAY-USHJOAKVSA-N
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Compound 16f
Molecular Weight:422.164
Molecular Formula:C17H18FeO9
InChIKey:WKWMMYKZIGZYRF-ZWACTXNCSA-N
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Compound 17a
Molecular Weight:293.074
Molecular Formula:C12H13FeO5
InChIKey:YPMYELKMOVQUNR-UHFFFAOYSA-N
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Compound 17b
Molecular Weight:318.083
Molecular Formula:C13H12FeNO5
InChIKey:YIMORKACKAVLNC-ADYBYETBSA-N
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Compound 17c
Molecular Weight:307.1
Molecular Formula:C13H15FeO5
InChIKey:VXDOGIVIOLDAMH-HMPSQKMJSA-N
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Compound 17d
Molecular Weight:401.235
Molecular Formula:C18H17FeO5S
InChIKey:QLLCGYXVSJZZNZ-HIOIQKJISA-N
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Compound 17e
Molecular Weight:309.073
Molecular Formula:C12H13FeO6
InChIKey:UMLQHEYSRGZEEY-PVLOTTOTSA-N
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Compound 17f
Molecular Weight:423.172
Molecular Formula:C17H19FeO9
InChIKey:IMLVSNWKVKNKJF-ZWRXAYIMSA-N
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  1. 1 - 47