Transformation of carbonyl to vinylidene groups in the π-conjugated peripheral substituent of chlorophyll derivatives by Tebbe reagent
2016
Tamiaki, Hitoshi | Tsuji, Kazuki | Machida, Shinnosuke | Teramura, Misato | Miyatake, Tomohiro
The 131-oxo-moiety of chlorophyll-a derivatives including methyl (pyro)pheophorbides-a, mesopyropheophorbide-a, and bacteriopheophorbide-d possessing vinyl, ethyl, and 1-hydroxyethyl groups, respectively, at the 3-position was transformed into the corresponding exo-methylene group by treatment of Tebbe reagent. The synthetic procedures were useful for the regioselective conversion of the carbonyl to vinylidene group at the 3-position and naturally occurring chlorophyll-d (3-CHO) was successfully modified to chlorophyll-a (3-CHCH2). Under the methylenation conditions, ester–carbonyl, hydroxy, and allyl groups in the peripheral substituents were tolerant as well as an acid-labile magnesium at the central position of chlorophylls.
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