Enantiopure cyclic O ‐substituted phenylphosphonothioic acid: Synthesis and chirality‐recognition ability

As a new acidic selector (resolving agent), we synthesized an enantiopure O ‐alkyl phenylphosphonothioic acid with a seven‐membered ring (( R )‐ 5 ), which was designed on the basis of the results for the enantioseparation of 1‐arylethylamine derivatives with acyclic O ‐ethyl phenylphosphonothioic acid ( I ). The phosphonothioic acid ( R )‐ 5 showed unique chirality‐recognition ability in the enantioseparation of 1‐naphthylethylamine derivatives, aliphatic secondary amines, and amino alcohols; the ability was complementary to that of I . The X‐ray crystallographic analyses of the less‐ and more‐soluble diastereomeric salts showed that hydrogen‐bonding networks in the salt crystals are 2 1 ‐column‐type with a single exception which is cluster‐type. In the cases of the 2 1 ‐column‐type crystals, stability of the crystals is firstly governed by hydrogen bonds to form a 2 1 ‐column and secondly determined by intra‐columnar T‐shaped CH/π interaction(s), intra‐columnar hydrogen bond(s), inter‐columnar van der Waals interaction and/or inter‐columnar T‐shaped CH/π interaction(s). In contrast, the cluster‐type salt crystal is stabilized by the assistance of inter‐cluster T‐shaped CH/π and van der Waals interactions. To realize still more numbers of intra‐ and inter‐columnar and ‐cluster T‐shaped CH/π interactions, the seven‐membered ring of ( R )‐ 5 plays a considerable role. Chirality 23:438–448, 2011. © 2009 Wiley‐Liss, Inc.