Computational Chemistry; A Useful Tool for the Chemical Synthesis of Complex Molecules, Heterocycles and Catalysts

Ana Arrieta; María C. de la Torre; Abel de Cózar; Miguel A. Sierra; Fernando P. Cossío

doi:10.1055/s-0032-1318217

Synlett, Table of Contents

Synlett 2013; 24(5): 535-549
DOI: 10.1055/s-0032-1318217

account

Computational Chemistry; A Useful Tool for the Chemical Synthesis of Complex Molecules, Heterocycles and Catalysts

Ana Arrieta

^aDepartamento de Química Orgánica I – Kimika Organiko I Saila, Facultad de Química – Kimika Fakultatea, Universidad del País Vasco – Euskal Herriko Unibertsitatea (UPV/EHU), P° Manuel de Lardizabal 3, 20018 San Sebastián-Donostia, Spain Fax: +34(943)015270 Email: fp.cossio@ehu.es

,

María C. de la Torre

^bInstituto de Química Orgánica General (IQOG), CSIC, Juan de la Cierva 3, 28006 Madrid, Spain

,

Abel de Cózar

^aDepartamento de Química Orgánica I – Kimika Organiko I Saila, Facultad de Química – Kimika Fakultatea, Universidad del País Vasco – Euskal Herriko Unibertsitatea (UPV/EHU), P° Manuel de Lardizabal 3, 20018 San Sebastián-Donostia, Spain Fax: +34(943)015270 Email: fp.cossio@ehu.es

^cIkerbasque, Basque Foundation for Science, 48011 Bilbao, Spain

,

Miguel A. Sierra

^dFacultad de Ciencias Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid, Spain

,

Fernando P. Cossío*

^aDepartamento de Química Orgánica I – Kimika Organiko I Saila, Facultad de Química – Kimika Fakultatea, Universidad del País Vasco – Euskal Herriko Unibertsitatea (UPV/EHU), P° Manuel de Lardizabal 3, 20018 San Sebastián-Donostia, Spain Fax: +34(943)015270 Email: fp.cossio@ehu.es

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Abstract

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Abstract

This Account describes our recent studies on the chemical synthesis of cyclic, densely substituted molecules by means of a hybrid approach consisting of the synergistic interaction between computational and experimental chemistry. In addition, two related total syntheses of complex molecules (±)-Scopadulin and (–)-Exiguolide are presented as case studies in which computational chemistry can be used to detect and, eventually, avoid potential failures involving key transformations of advanced intermediates.

1 Introduction

2 Computational Treatment of Molecules

3 Computational Characterization of Reactants, Reaction Intermediates, Products and Transition Structures

4 Computational–Experimental Analysis of the Stereocontrol in Thermal Pericyclic Reactions

4.1 Concerted and Stepwise [3+2] Cycloadditions

4.2 Concerted and Stepwise [8+2] Cycloadditions

5 Total Synthesis of Complex Molecules; Two Case Studies

5.1 Total Synthesis of (±)-Scopadulin

5.2 Total Synthesis of (–)-Exiguolide

6 Conclusions and Outlook

Key words

pericyclic reactions - cycloaddition - asymmetric catalysis - antitumor agents - metathesis - Michael addition - ring closure - ylides

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References

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