Synthesis of redox derivatives of lysine and related peptides containing phenothiazine or tris(2,2'-bipyridine)ruthenium(II).
Boc-L-Lysine derivatives and lysine-containing peptides bearing the electron donor 10H-phenothiazine (PTZ) or the redox chromophore tris(2,2'-bipyridine)ruthenium(II) dication ([Rub3]2+, where b is 2,2'-bipyridine) have been synthesized and characterized. SeO2 oxidation (53% yield) of 4,4'-dimethyl-2,2'-bipyridine, Ag2O oxidation (85% yield) of the monoaldehyde, complexation (96% yield) of 4'-methyl-2,2'-bipyridine-4-carboxylic acid (m-OH) with Rub2Cl2, activation (81% yield) of the acid [Rub2m-OH]2+ (PF6-)2, and condensation (83% yield) of the succinimido ester [Rub2m-OSu]2+ (PF6-)2 with Boc-Lys furnished the protected redox-chromophore module [Boc-Lys(Rub2m)-OH]2+ (PF6-)2 in 29% overall yield over five steps. The first two steps constitute the first practical synthesis of the monocarboxylic acid m-OH (45% overall yield). Also prepared were m-OSu, Boc-Lys(m)-OH, Boc-Lys(m)-OCH3, and [Rub2m-NHCH3]2+ (PF6-)2. Activation (91% yield) of 3-(10H-phenothiazine-10)propanoic acid (PTZpn-OH) and condensation (92% yield) of the succinimido ester PTZpn-OSu with Boc-Lys furnished the protected electron-donor module Boc-Lys(PTZpn)-OH (84% overall yield). The latter was used in solid-phase syntheses of two redox tripeptides, CH3CO-Ala-Lys(PTZpn)-Ala-OH and [Rub2m-Ala-Lys(PTZpn)-Ala-OH]2+ (PF6-)2. The electrochemical properties of these redox amino acids and peptides were similar to those of PTZpn-OH, [Rub2m-OH]2+ (PF6-)2, or [Rub2m-NHCH3]2+ (PF6-)2. Lys(PTZpn), [Lys(Rub2m)]2+ (PF6-)2, and other redox modules may be useful for engineering light-harvesting proteins, photovoltaic cells, and other molecular electronic devices.
Peek
B M
BM
Department of Chemistry, University of North Carolina, Chapel Hill.
Ross
G T
GT
Edwards
S W
SW
Meyer
G J
GJ
Meyer
T J
TJ
Erickson
B W
BW
D015082:2,2'-Dipyridyl / Q000031:analogs & derivatives* / Q000737:chemistry; D056831:Coordination Complexes; D004560:Electricity; D008239:Lysine / Q000031:analogs & derivatives*; D008956:Models, Chemical; D010084:Oxidation-Reduction; D010455:Peptides / Q000737:chemistry; D010640:Phenothiazines / Q000737:chemistry*; D010777:Photochemistry / Q000379:methods*; D010860:Pigments, Biological; D011199:Potentiometry; D017975:Ruthenium Compounds
D015082:2,2'-Dipyridyl; D056831:Coordination Complexes; D008239:Lysine; D010455:Peptides; D010640:Phenothiazines; D010860:Pigments, Biological; C547232:tris(2,2-bipyridine)-ruthenium(II); D017975:Ruthenium Compounds