Absolute configuration at a sulfenamide chiral axis. Crystal and molecular structure of N-(1-.alpha.-naphthylethyl)-N-(benzenesulfonyl)trichloromethanesulfenamide

Abstract

The crystal structure of 7V-(l-a-naphthylethyl)-iV-(benzenesulfonyl)trichloromethanesulfenamide has been determined by three-dimensional X-ray diffraction. The molecule crystallizes in space group P2j with lattice constants a = 12.233 (6) Á, b = 8.546 (5) Á, c = 10.440 (5) Á, ß = 110.20 (1) °,Z = 2. Refinement of 1536 diffractometer data yielded a conventional discrepancy factor of 0.075. The structure found, which features a nearly planar trivalent nitrogen atom, has implications concerning torsional isomerism about heteroatom-heteroatom bonds (in this case between trivalent nitrogen and divalent sulfur) and concerning the possible existence of p-d ttbonding in S-N bonds. The incorporation of an asymmetric carbon atom of known configuration allowed the assignment of absolute configuration to the sulfenamide chiral axis.he structure and conformational analysis of molecules with sulfur-nitrogen bonds has been a topic of recent interest. A number of X-ray crystallographic structure determinations of molecules with different kinds of sulfur nitrogen bonds have appeared.2-4 In (1) This work was supported in part by grants from the National Science Foundation (No. GP-17092 and GP-15070) and the Edmond de Rothschild Foundation. We thank the Wayne State University Computing and Data Processing Center for the use of their facilities.(2) (a

A Pseudohypervalent Sulfur Intermediate as an Oxidative Protective Mechanism in the Archaea Peroxiredoxin Enzyme ApTPx

“…Instead, they proposed that a neutral C p thiol reduces the peroxide with concomitant formation of the sulfurane intermediate (Scheme ). A similar S–N interaction involving a histidyl was previously reported in human 1-Cys Prx (hORF6), although the observed distance was suggested to instead reflect a hydrogen-bonding interaction. , It is noted, however, that a covalent single S–N bond length in sulfenamides is typically in the vicinity of 1.7 Å. , …”

The chemistry of sulfenamides

“…The X-ray crystal structure of sulfenamide 15 reveals a nearly planar configuration around nitrogen (the sum of the bond angles at nitrogen is 356.5°), with the C-S-N plane perpendicular to the plane of the two nitrogen substituents. 24 The X-ray structure of sulfenamide 9, however, indicates a pyramidal sulfenamide nitrogen.18…”

Barriers to nitrogen inversion in cyclic and acyclic substituted hydroxylamines. A theoretical study

“…An x-ray crystallographic structure determination of a related compound, a sulfenamide, similarly featured a Y conformation along the N-S bond in the Newman projection. 20 The ground state conformation 2a serves as a cyclic model and has dihedral angles of = 0°and = 58.2°. This point lies very close to the torsional energy maximum which occurs at = 5°, = 63°.…”