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Rearrangement of S ‐(2‐Aminoethyl) Thiophosphates to N ‐(2‐Mercaptoethyl)phosphoramidates
Author(s) -
Chen Menglin,
Maetzke Alice,
Knak Jensen Svend J.,
Gothelf Kurt V.
Publication year - 2007
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200700646
Subject(s) - chemistry , solvent , medicinal chemistry , reaction mechanism , alkylation , computational chemistry , density functional theory , hydrolysis , molecule , thiol , organic chemistry , catalysis
A novel rearrangement of S ‐(2‐aminoethyl) thiophosphates to N ‐(2‐mercaptoethyl)phosphoramidates was discovered and developed. The reaction proceeds smoothly at room temperature under basic conditions and the resulting thiol could subsequently be alkylated. The reaction mechanism is investigated by electron structure calculations using density functional theory at the B3LYP/6‐31G(d) and B3LYP/6‐311+G(d,p) levels. The calculations indicate that the reaction proceeds in a two step process when two explicit solvent molecules are included. In the presence of water the rearrangement reaction proceeds in competition with hydrolysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)