DABCO and DMAP—Why Are They Different in Organocatalysis?

Abstract

What makes a good organocatalyst? DABCO (1,4-diazabicyclo[2.2.2]octane) is a thousandfold better nucleophile (k→) and at the same time a million times better leaving group (k←) than DMAP (4-(dimethylamino)pyridine). This apparent contradiction is resolved by consideration of the intrinsic reaction barriers. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2007/z701489_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.