Issue 10, 2013
From the journal:

Chemical Science

Carbonium vs. carbenium ion-like transition state geometries for carbocation cyclization – how strain associated with bridging affects 5-exo vs. 6-endo selectivity†

Osvaldo Gutierrez,a   Jason G. Harrison,a   Ryan J. Felix,b   Fernando Cortés Guzman,c   Michel R. Gagné*b  and  Dean J. Tantillo*a  

* Corresponding authors

a Department of Chemistry, University of California–Davis, 1 Shields Avenue, Davis, CA 95616, USA
E-mail: djtantillo@ucdavis.edu

b Department of Chemistry, University of North Carolina at Chapel Hill, North Carolina 27599-3190, USA
E-mail: mgagne@unc.edu

c Instituto de Química, Universidad Nacional Autónoma de México, México D.F. 04510, Mexico

Abstract

Quantum chemical calculations are used to explore the origins of regioselectivity for proton-, Pt(II)- and Pd(II)-promoted cyclizations of 1,5-hexadienes, 5-aminoalkenes, and allylic acetimidates. The strain associated with achieving carbonium ion-like transition state geometries is shown to be a key factor in controlling 5-exo vs. 6-endo selectivity.

Graphical abstract: Carbonium vs. carbenium ion-like transition state geometries for carbocation cyclization – how strain associated with bridging affects 5-exo vs. 6-endo selectivity

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Article information

DOI
https://doi.org/10.1039/C3SC51657A
Article type
Edge Article
Submitted
13 Jun 2013
Accepted
19 Jul 2013
First published
22 Jul 2013

Chem. Sci., 2013,4, 3894-3898

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Carbonium vs. carbenium ion-like transition state geometries for carbocation cyclization – how strain associated with bridging affects 5-exo vs. 6-endo selectivity

O. Gutierrez, J. G. Harrison, R. J. Felix, F. Cortés Guzman, M. R. Gagné and D. J. Tantillo, Chem. Sci., 2013, 4, 3894 DOI: 10.1039/C3SC51657A

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