Synthesis and characterization of chlorophyll a enol derivatives: Chlorophyll a tert-butyldimethylsilyl-enol ether and 131-deoxo-131, 132-didehydro-chlorophyll a

Abstract

Using the sterically hindered base, 1,8-diazabicyclo[5.4.0]undec-7-ene, for enolization and tert-butyldimethylsilyl-trifluoromethanesulfonate for silylation, chlorophyll (Chl) [Formula: see text] produced after 15 min at 0 [Formula: see text]C in deaerated pyridine solution under argon, after work-up and chromatographic purification on a sucrose column, tert-butyldimethylsilyl-enol ether of Chl [Formula: see text] in a yield of 77%. The 131-deoxo-131,132-didehydro-chlorophyll [Formula: see text], was obtained in a yield of 23% through a reaction sequence, where Chl [Formula: see text] was first reduced with sodium borohydride to 13[Formula: see text]-hydroxy-Chl [Formula: see text], which via demetalation yielded 13[Formula: see text]-hydroxypheophytin [Formula: see text]. In the presence of the sterically hindered base, 1,8-bis(dimethylamino)naphthalene, trifluoroacetylimidazole dehydrated 13[Formula: see text]-hydroxypheophytin [Formula: see text] to 131-deoxo-131,132-didehydro-pheophytin [Formula: see text], which after metalation yielded 131-deoxo-131,132-didehydro-Chl [Formula: see text]. Using 1,8-bis(dimethylamino)naphthalene and trifluoroacetylimidazole, the straight conversion of 13[Formula: see text]-hydroxy-Chl [Formula: see text] to 131-deoxo-131,132-didehydro-Chl [Formula: see text] was found unsuccessful. The major products were characterized by electronic absorption spectra (UV-vis) and practically completely assigned 1H and [Formula: see text]C NMR spectra. Some intermediates of the syntheses were also characterized by ESI-TOF mass spectra. Compared with Chl [Formula: see text], the macrocyclic ring-current in the synthesized Chl [Formula: see text] enol derivatives was found weakened by the expansion of the [Formula: see text]-system to include the isocyclic ring E. Nevertheless, these enol derivatives were still considered to be diamagnetic and aromatic. The possibility of the functional role of the enol derivatives of chlorophyll in photosynthesis is discussed.