Mild and Safer Preparative Method for Nonsymmetrical Sulfamides via N-Sulfamoyloxazolidinone Derivatives:  Electronic Effects Affect the Transsulfamoylation Reactivity

Abstract

Sulfamides (R 1 R 2 N-SO 2 -NR 3 R 4 ) are traditionally prepared by using strong electrophilic and hazardous reagents such as N-sulfamoyl chloride, sulfonyl chloride, phosphorus oxychloride, or phosphorus pentachloride. We report here a safer and more convenient synthetic methodology for large-scale preparation of sulfamides using the N-substituted oxazolidin-2-one derivatives 5 as synthetic equivalent of the corrosive and hazardous N-sulfamoyl chloride. The scope of the use of N-sulfamoyloxazolidinones to prepare nonsymmetrical sulfamides is explored.

Bis‐Sulfamyl Imines: Potent Substrates for Asymmetric Additions of Arylboroxines under Rhodium Catalysis

“…Aryl‐Grignard addition to the imines gave a 1:1 mixture of diastereomers which could be separated by chiral HPLC but in most cases are identical by 1 H NMR. Synthesis of the achiral meso ‐diastereoisomer via an N ‐sulfamoyloxazolidinone intermediate,12 7 (Scheme ) confirmed the identity of the three peaks seen in the chiral HPLC chromatograph.…”

Rationally Designed Sulfamides as Glutamate Carboxypeptidase II Inhibitors

“…A simple method, amenable to parallel synthesis, was employed to synthesize the sulfamide inhibitor library (Scheme 1). The common oxazolidinone intermediate and sulfamides were synthesized as outlined by Borghese and coworkers with minor modifications . Briefly, commercially available chlorosulfonyl isocyanate was treated with 2‐bromoethanol or benzyl alcohol, followed by treatment with diprotected glutamic acid ( 8 or 9 ) to generate the oxazolidinone intermediates 4 or 5 and Cbz‐glutamyl sulfamide 7 , respectively.…”

Implementation of Diverse Synthetic and Strategic Approaches to Biologically Active Sulfamides

“…Application of an oxazolidinone as sulfamoylation agent (refer to scheme 4 in asymmetric sulfamide section) for the preparation of the cyclic sulfamide 62.4 is shown in Scheme 62 [32b] . Mixture of two isomers 62.2 : 62.3 (Yield ratio: 75/25) was furnished from the vicinal diamine 62.1 .…”