Jump to main content
Jump to site search

Issue 5, 2012
Previous Article Next Article

The intramolecular Diels–Alder reaction of tryptamine-derived Zincke aldehydes is a stepwise process

Author affiliations

Abstract

Computational studies show that the base-mediated intramolecular Diels–Alder of tryptamine-derived Zincke aldehydes, used as a key step in the synthesis of the Strychnos alkaloids norfluorocurarine and strychnine, proceeds via a stepwise pathway. The experimentally determined importance of a potassium counterion in the base is explained by its ability to preorganize the Zincke aldehyde diene in an s-cis conformation suitable to bicyclization. Computation also supports the thermodynamic importance of the generation of a stable enolate in the final reaction step. The thermal cycloreversion reaction of the Diels–Alder products is also found to proceed in a stepwise manner.

Graphical abstract: The intramolecular Diels–Alder reaction of tryptamine-derived Zincke aldehydes is a stepwise process

Back to tab navigation

Supplementary files

Article information


Submitted
18 Dec 2011
Accepted
01 Feb 2012
First published
02 Feb 2012

Chem. Sci., 2012,3, 1650-1655
Article type
Edge Article

The intramolecular Diels–Alder reaction of tryptamine-derived Zincke aldehydes is a stepwise process

H. V. Pham, D. B. C. Martin, C. D. Vanderwal and K. N. Houk, Chem. Sci., 2012, 3, 1650
DOI: 10.1039/C2SC01072K

Social activity

Search articles by author

Spotlight

Advertisements