Conformational study of eight-membered diazocine turn mimics by two-dimensional NMR spectroscopy.
The eight-membered ring conformations of two diazocine turn mimics, methyl-[2,5-dioxo-3-(S)-(3-omega-tosyl-guanidino-propyl)-4-methyl-octahy dro- 1,4-diazocin-1-yl]acetate (I) and methyl-[2,5-dioxo-3-(S)-(3-omega-tosyl-guanidino-propyl)-octahydro-1,4- diazocin-1-yl]acetate (II), were determined using torsion angle constraints derived from 3J(C,H) coupling constants extracted from 13C-filtered TOCSY spectra with 13C in natural abundance. For I, the torsion angle constraints derived from 3J(C,H) coupling constants were in agreement with torsion angle constraints derived from 3J(H,H) coupling constants extracted from a P.E. COSY spectrum. Similar 3J(C,H) coupling constants were found for I and II, and they shared an identical eight-membered ring conformation characterized by two cis-amide bonds and a staggered conformation of the trimethylene group in which the H3 proton is proximal to both the H6 and H8 protons.
Bean
J W
JW
Department of Physical & Structural Chemistry, SmithKline Beecham Pharmaceuticals, King of Prussia, PA 19406-0939.
Briand
J
J
Burgess
J L
JL
Callahan
J F
JF
D001392:Azocines / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009842:Oligopeptides / Q000737:chemistry; D011487:Protein Conformation
D001392:Azocines; D009842:Oligopeptides; C090360:methyl (2,5-dioxo-3-(3-(tosylguanidino)propyl)-4-methyl-octahydro-1,4-diazocin-1-yl)acetate; C090361:methyl-(2,5-dioxo-3-(3-(tosylguanidino)propyl)-octahydro-1,4-diazocin-1-yl)acetate; C047981:arginyl-glycyl-aspartic acid