Skip to main content
SpringerLink
Log in
Book cover

Organometallics in Organic Synthesis pp 277–295Cite as

A Zinc Mediated Route from α-Imino Esters to β-Lactams

  • Conference paper

Abstract

In the course of our studies on the coordination behavior of 1,4-dihetero-1,3-butadienes towards Li-, Cu-, Zn-, A1-, and Sn-organometallic compounds, it became obvious that in many cases these substituted 1,4-dihetero-1,3-butadiene molecules (Table 1) are converted selectively into organic compounds containing either two equivalent or two different α-positioned heteroatoms. Up still now, little effort appears to have been put into exploring this particular synthetic route.

This is a preview of subscription content, log in via an institution.

Chapter
USD   29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD   84.99
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD   109.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Learn about institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  • Ashby EC, Goel AB (1981) Direct evidence supporting a single-electron transfer pathway in the reduction of ketones by primary, secondary, and tertiary Grignard reagents. J Am Chem Soc 103: 4983–4985

    Article  CAS  Google Scholar 

  • Brockmann M, torn Dieck H (1986) Synthese silylierter enanime durch rhodium-katalysierte hydrosilylierung von 1-aza- und l,4-diaza-l, 3-dienen. J Organometal Chem 314: 75–83

    Article  CAS  Google Scholar 

  • Chanon M (1987) Electron-transfer-induced chain reactions and catalysis. Building bridges between inorganic, organic, and organometallic substrates. Acc Chem Res 20: 214–221

    Article  CAS  Google Scholar 

  • tom Dieck H, Dietrich J (1984) Synthesis of chiral diazadienes R*-N=CR-′CR′=N-R*. Chem Ber 117: 694–701

    Article  Google Scholar 

  • Fonseca I, Martinez-Carrera S, Garcia-Blanco S (1979) Crystal structure and absolute configuration of α-(l-phenylethylimino)benzyl phenyl ketone. Acta Cryst B35: 2643–2646

    Article  CAS  Google Scholar 

  • Jastrzebski JTBH, Klerks JM, van Koten G, Vrieze K (1981) An unexpected ethyl transfer reaction between Et2Zn and di(t-butyl)-glyoxaldiimine (t- BuDAB). Studies of the persistent (EtZn(f-BuDAB)] radical which is in equilibrium with its C-C coupled dimer. J Organometal Chem 210: C49–C53

    Article  CAS  Google Scholar 

  • Jastrzebski JTBH, van der Steen FH, van Koten G (1987) Selective formation of 1, 3, 4-trisubstituted and 3, 4-disubstituted trans-β-lactams from zinc enolates and imines (in press Reel Trav Chim Pays-Bas)

    Google Scholar 

  • Jastrzebski JTBH, van Koten G, van de Mieroop WF (1987) X-ray crystal structure of the hexameric lithium enolate of ethyl NJV-diethylglycinate (in press Inorg Chim Acta)

    Google Scholar 

  • Kaim W (1985) Radical forming electron-transfer reactions involving main-group organometallics. Acc Chem Res 18: 160 - 167

    Article  CAS  Google Scholar 

  • Keijsper J, van der Poel H, Polm LH, van Koten G, Vrieze K (1983) Comparison of free and metal coordinated 1, 4-disubstituted l, 4-diaza-l, 3-butadienes. Crystal and molecular structures of l,4-dicyclohexyl-l,4-diaza-l,3-butadiene and trans-[dichloro(triphenylphosphine)- (1,4-di-tert-buty 1-1,4-diaza-1,3-butadiene)palladium(II)]. Polyhedron 2: 1111–1116

    Article  CAS  Google Scholar 

  • Klerks JM, Stufkens DJ, van Koten G, Vrieze K (1979) Diazabutadienes as ligands. I. Compounds of aluminium: Coordination of diazabutadienes to A1(CH3)3 and subsequent intramolecular insertion and rearrangement reactions leading to (CH3)2A1-RN-CH(CH3)-C(R′)=N-R(R′= H, CH3) and (CH3)2A-RN-CH2-C(CH3)=N-R. J Organometal Chem 181: 271–283

    Article  CAS  Google Scholar 

  • Klerks JM, Jastrzebski JTBH, van Koten G, Vrieze K (1982) Regioselective ethyl transfer reactions between diethylzinc and l, 4-dialkyl-l, 4-diaza-l, 3-butadienes: Synthesis of EtZn[R(Et)NCH=CHNR]. J Organometal Chem 224: 107–119

    Google Scholar 

  • van Koten G, Vrieze K (1982) l,4-Diaza-l,3-butadiene (α-diimine) ligands: Their coordination modes and the reactivity of their metal complexes.In: Stone FGA, West R (ed) Advances in Organometallic Chemistry, vol 21. Academic Press, New York, p 152

    Google Scholar 

  • van Koten, Jastrzebski JTBH, Vrieze K (1983) Stable l, 4-diaza-l, 3-butadiene (a-diimine)zinc and -aluminium radicals formed in single electron transfer reactions: Their consequences for organic syntheses. J Organom tal Chem 250: 49–61

    Google Scholar 

  • van der Poel H, van Koten G (1978) Synthesis and characterization of l-iminopropan-2-one and 2-iminobutan-3-one compounds, RC(O)C(NR′)R′′. Synthetic Comm 8: 305–313

    Article  Google Scholar 

  • van der Poel H, van Koten G, Vrieze K (1980) Novel bonding modes of a-diimines. Synthesis and characterization of [MCl2L(a-diimine)] and [MCl2(oc-diimine)n] (M = Pd, Pt; L = Phosphine, Arsine; n =1, 2) containing σ,σ-N,N′, σ.-N, or σ-N ↔ σ-N′ bonded α-diimines. Inorg Chem 19: 1145–1151

    Google Scholar 

  • Spek AL, Jastrzebski JTBH, van Koten G (1987) Structure of diethyl[μ-N,μ.-N′-(1, 2-di-t-butylamino)-σ-N,σ-N′-1,2-di(2-pyridyl)ethane]dizinc (submitted Acta Cryst)

    Google Scholar 

  • van Vliet MRP, Jastrzebski JTBH, van Koten G, Vrieze K (1983) Novel reactions of substituted 1 -aza-4-oxobutadienes (a-imino ketones) with diorganozinc reagents. Selective ethyl transfer in the Et2Zn/t-BuN=C(H)-C(Me)=O system and X-ray crystal structure of [EtZn(Et)(t-Bu)NC(H)=C(Me)O]2. J Organometal Chem 251: C17–C21

    Article  Google Scholar 

  • van Vliet MRP, van Koten G, Rotteveel MA, Schrap M, Vrieze K (1986) Reactivity of l-aza-4-oxo-1.3-butadienes (α-imino ketones) toward triorganoaluminum reagents. 1. X-ray crystal structures of [(AlMe3)2σ, σ-N,O-(MeN=C(Ph)C(Ph)=O)], with a N,O-bridge-bonded α-imino ketone, and of Me2Al(t-Bu)N=CHC(Me)2OAlMe3, a carbonyl alkylated product which is O-coordinated to AlMe3. Organometallics 5: 1389 - 1394

    Article  Google Scholar 

  • van Vliet MRP, van Koten G, van Beek JAM, Vrieze K, Muller F, Stam CH (1986) Monodentate-N coordination of l-aza-4-oxo-1, 3-butadienes [R1N=C(R2)C(R3)=O] to platinum(II). X-ray structure of trans-[PtCl2(PEt3)σ-N-(t-BuN=CHC(Me)=O]. Inorg Chim Acta 112: 77–85

    Article  Google Scholar 

  • van Vliet MRP, Jastrzebski JTBH, Klaver WJ, Goubitz K, van Koten G (1987) The unexpected formation of trans β-lactams in the reaction of α-iminoesters (R-N=C(H)C(=O)OR′) with diethylzinc. Crystal structure of trans-l-(N-t-butyl)-3-(N-t-butyl-N-ethylamino)- -4-methoxycarbonylazetidin-2-one (submitted Reel Trav Chim Pays-Bas)

    Google Scholar 

  • van Vliet, MRP, van Koten G, Buysingh P, Jastrzebski JTBH, Spek AL (1987) Reactivity of l-aza-4-oxa- 1,3-butadienes (α-imino ketones) toward diorganozinc reagents: regio- ana chemoselective transfer of organo groups in the ZnR2/R1N=C(R2)C(R3)=O system and X-ray structure of the organozinc enolate [EtZn(Et)(t-Bu)NCH(H) = C(Me)6]2. Organometallics 6: 537–546

    Article  Google Scholar 

  • van Vliet MRP, van Koten G, Modder JF, van Beek JAM, Klaver WJ, Goubitz K, Stam CH (1987) Coordination of 3-substituted l-aza-4-oxo-1,3-butadienes (a-iminoesters and amides) to aluminum and zinc chloride and to dimethylzinc. Selective reduction in the ZnEt2-R1N=CHC(NEt2)=O system, and crystal structure of [EtZn(t-Bu)NCH2C(NEt2)=O]2. J Organometallic Chem 319: 285–301

    Article  Google Scholar 

  • van Vliet MRP, van Koten G, de Keijser MS, Vrieze K (1987) Reactivity of l-aza-4-oxa-1, 3-butadienes (α-imino ketones) toward triorganoaluminum reagents. 2. Syntheses of triorganoaluminum a-imino ketone coordination complexes, diorganoaluminum (a-imino)alkoxides, and diorganoaluminum (α-imino)enolates and study of their dynamic behavior in solution and 13C NMR) (in press Organometallics)

    Google Scholar 

  • Zettlitzer M, torn Dieck H, Haupt ETK, Stamp L (1986) Synthese 2-funktionalisierter N,N′ -dialkyl- -imidazoliumsalze aus glyoxal und alkylaminen. Chem Ber 119: 1868–1875

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Laboratory of Organic Chemistry, University of Utrecht, 3584 CH, Utrecht, The Netherlands

    Gerard Van Koten

Authors
  1. Gerard Van Koten
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. Institute for Organic Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, D-2000, Hamburg 13, Germany

    Armin de Meijere

  2. Institute for Inorganic and Applied Chemistry, University of Hamburg, Martin-Luther-King-Platz 6, D-2000, Hamburg 13, Germany

    Heindirk tom Dieck

Rights and permissions

Reprints and permissions

Copyright information

© 1987 Springer-Verlag Berlin Heidelberg

About this paper

Cite this paper

Van Koten, G. (1987). A Zinc Mediated Route from α-Imino Esters to β-Lactams. In: de Meijere, A., tom Dieck, H. (eds) Organometallics in Organic Synthesis. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-73196-9_15

Download citation

  • DOI: https://doi.org/10.1007/978-3-642-73196-9_15

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-18592-5

  • Online ISBN: 978-3-642-73196-9

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation