Getting round the (periodic) table: A highly chemo- and enantioselective conjugate addition of diphenylphosphine to α,β-unsaturated aldehydes in the presence of a chiral secondary amine C provides a direct route to chiral β-phosphino aldehyde intermediates (see scheme, TMS=trimethylsilyl). The synthetic utility of the strategy was exemplified in a rapid one-pot (two-step) synthesis of highly enantioenriched 3-aminophosphines. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2007/z700754_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.