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Computational Studies on the Synthesis of β-Lactams via [2+2] Thermal Cycloadditions

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Heterocyclic Scaffolds I

Part of the book series: Topics in Heterocyclic Chemistry ((TOPICS,volume 22))

Abstract

The main computational studies on the formation of β-lactams through [2+2] cycloadditions published during 1992–2008 are reported with special emphasis on the mechanistic and selectivity aspects of these reactions. Disconnection of the N1-C2 and C3–C4 bonds of the azetidin-2-one ring leads to the reaction between ketenes and imines. Computational and experimental results point to a stepwise mechanism for this reaction. The first step consists of a nucleophilic attack of the iminic nitrogen on the sp-hybridized carbon atom of the ketene. The zwitterionic intermediate thus formed yields the corresponding β-lactam by means of a four-electron conrotatoty electrocyclization. The steroecontrol and the periselectivity of the reaction support this two-step mechanism. The [2+2] cycloaddition between isocyanates and alkenes takes place via a concerted (but asynchronous) mechanism that can be interpreted in terms of a [π2s + (π2s + π2s)] interaction between both reactants. Both the regio and the stereochemistry observed are compatible with this computational model. However, the combination of solvent and substituent effects can result in a stepwise mechanism.

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Abbreviations

AM1:

Austin Model 1

B3LYP:

Hybrid three-parameter functional derived by Becke, Lee, Yang and Parr

CASSCF:

Completely active space self-consistent field

CI-HE:

Configuration interaction-half electron method

DFT:

Density-functional theory

ECP:

Effective core potential

MNDO:

Minor neglect of differential overlap

MO:

Molecular orbital

MPn :

n th order Møller-Plesset expansion

PCM:

Polarization continuum model

PM3:

Third parametrization of MNDO

RHF:

Restricted Hartree-Fock

SCF:

Self-consistent field

SCRF:

Self-consistent reaction field

UHF:

Unrestricted Hartree-Fock

ZPVE:

Zero-point vibrational energy

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Authors and Affiliations

  1. Departamento de Química Orgánica I, Kimika Organikoa Saila I, Universidad del País Vasco – Euskal Herriko Unibertsitatea, 1072, 20080, San Sebastián-Donostia, Spain

    Ana Arrieta, Begoña Lecea & Fernando P. Cossío

  2. DIPC, Pº Manuel de Lardizabal 4, Universidad del País Vasco – Euskal Herriko Unibertsitatea, 20018, San Sebastián-Donostia, Spain

    Ana Arrieta, Begoña Lecea & Fernando P. Cossío

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  1. Ana Arrieta
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  2. Begoña Lecea
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  3. Fernando P. Cossío
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Correspondence to Fernando P. Cossío .

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Editors and Affiliations

  1. Dept. Chemistry, University of Texas-Pan American, W. University Drive 1201, Edinburg, 78539, USA

    Bimal K. Banik

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Arrieta, A., Lecea, B., Cossío, F.P. (2010). Computational Studies on the Synthesis of β-Lactams via [2+2] Thermal Cycloadditions. In: Banik, B. (eds) Heterocyclic Scaffolds I. Topics in Heterocyclic Chemistry, vol 22. Springer, Berlin, Heidelberg. https://doi.org/10.1007/7081_2009_10

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