TY - JOUR A1 - Lindner, Christoph A1 - Tandon, Raman A1 - Maryasin, Boris A1 - Larionov, Evgeny A1 - Zipse, Hendrik T1 - Cation affinity numbers of Lewis bases JF - Beilstein Journal of Organic Chemistry PY - 2012/// VL - 8 SP - 1406 EP - 1442 SN - 1860-5397 DO - 10.3762/bjoc.8.163 PB - Beilstein-Institut JA - Beilstein J. Org. Chem. UR - https://doi.org/10.3762/bjoc.8.163 KW - ab initio KW - cation affinity KW - Lewis basicity KW - organocatalysis KW - proton affinity N2 - Using selected theoretical methods the affinity of a large range of Lewis bases towards model cations has been quantified. The range of model cations includes the methyl cation as the smallest carbon-centered electrophile, the benzhydryl and trityl cations as models for electrophilic substrates encountered in Lewis base-catalyzed synthetic procedures, and the acetyl cation as a substrate model for acyl-transfer reactions. Affinities towards these cationic electrophiles are complemented by data for Lewis-base addition to Michael acceptors as prototypical neutral electrophiles. ER -